Flexible polypropylene resins, propylene based elastomer compositions and process for production of olefin polymers

ABSTRACT

Disclosed are a flexible polypropylene resin suitable as thermoplastic elastomer, a propylene based elastomer composition containing the flexible polypropylene resin, and a process for producing the above flexible polypropylene resin and the propylene based elastomer composition. The above flexible polypropylene resin is composed of specific boiling heptane-soluble polypropylene and specific boiling heptane-insoluble polypropylene. The above propylene based elastomer composition comprises the above flexible polypropylene resin and an ethylene/propylene copolymer or an ethylene/propylene/polyene copolymer. The above process for the production of olefin polymers may be carried out by non-solvent polymerization methods such as a gas phase one-step polymerization method, and a gas phase multi-step polymerization method, using a specific catalyst.

This application is a Continuation-in-Part application of applicationSer. No. 08/450,711, filed May 25, 1995, now abandoned, the contents ofwhich are incorporated herein by reference in their entirety, which is aContinuation application of application Ser. No. 08/105,127, filed Aug.12, 1993 now abn. which application is a Divisional application ofapplication Ser. No. 07/730,807, filed Jul. 26, 1991 now abn., which wasfiled as PCT International Application No. PCT/JP90/01216 on Sep. 21,1990.

BACKGROUND OF THE INVENTION

The present invention relates to a novel, flexible polypropylene resinsuitable as thermoplastic elastomer material, and a propylene basedelastomer composition containing the polypropylene resin. The presentinvention also relates to a process for producing an olefin polymer,which may be suitably used for producing the above flexiblepolypropylene resin and the propylene based elastomer.

Thermoplastic elastomers have been widely used, as energy saving orresource saving type elastomers, for automotive parts, industrialmachine parts, electric or electronic parts, construction materials,especially, as replacement for vulcanized rubbers.

In general, olefin based thermoplastic elastomers (TPO) have beenproduced by a process comprising blending polypropylene and anethylene-propylene-diene rubber (EPDM) in the presence of peroxide. Suchprocess is described in, for example, Japanese Patent ApplicationLaid-Open Gazette (Kokai) N. 61-217747. However, this process isdisadvantageous since it requires complicated procedures and is a costlyprocess.

On the other hand, several attempts have been made to lower theproduction cost, by directly polymerizing a high molecular weightpolymer having dynamic properties similar to those of the above TPO. Forexample, Kokai 49-53983 and Japanese Patent Application PublicationGazette (Kokoku) No. 62-19444 propose a propylene-hexene copolymer, andKokai 61-179247 proposes an elastomeric polypropylene. However, thesepolymers are inferior in low temperature properties.

Further, as a method of improving polypropylene in low temperatureproperties, a two-step propylene/ethylene-propylene polymerization iswell known as described in, for example, Kokai 57-50804. However, it isdifficult to produce vulcanized rubber like polymer having flexibilityand tensile strength sufficient enough for practical use.

On the other hand, polypropylene has been produced using a Ziegler typecatalyst. In this case, mainly crystalline isotactic polypropylene isproduced with about 10 to 15% of atactic polypropylene as by-product.The atactic polypropylene has a low number average molecular weight (Mn)about 10,000, and thus are not suitable for practical use.

In the meanwhile, the present inventors found that atactic polypropylenehaving high molecular weight can be readily produced by polymerizingpropylene using a catalyst system comprising combination of a solidcatalyst component containing, as essential components, magnesium,titanium, a halogen atom and an electron donor; an organoaluminumcompound; and an alkoxy group-containing aromatic compound (Kokai63-243106). The atactic polypropylene is characterized by being solubleto boiling heptane; having a high molecular weight of, generally, 25,000to 100,000; and having a relatively narrow molecular weightdistribution. The atactic polypropylene has good melting properties asrubber like elastomer. However, the atactic polypropylene has poormechanical strength, resulting in, when used alone, restriction inapplication for molded materials.

In view of the above situations, it is an object of the presentinvention to provide a flexible polypropylene resin having excellentdynamic properties as thermoplastic elastomer and having good costperformance, which can be used for, e.g., automotive parts, industrialmachine parts, electric or electronic parts and construction materials.

It is another object of the present invention to provide a propylenebased elastomer composition having, even without being vulcanized,tensile strength sufficient enough for practical use; having sufficientflexibility and low temperature properties; having low surfacetackiness; and having good cost performance.

It is further object of the present invention to provide a process forproducing an olefin polymer, which can be used for producing the aboveflexible polypropylene resin and the propylene based elastomercomposition.

The present inventors made intensive studies to achieve the aboveobjects, as a result of the studies, it was found that the above objectscan be achieved by a flexible polypropylene containing, at a specificratio, atactic polypropylene having specific molecular weight andspecific molecular weight distribution and crystalline isotacticpolypropylene having specific melt-index; and a flexible polypropylenecontaining, at a specific ratio, atactic polypropylene component havingspecific intrinsic viscosity and isotactic polypropylene having specificintrinsic viscosity.

Further, the present inventors found that an elastomer compositionhaving physical properties similar to those of the TPO (partiallycross-linked) can be obtained by the use of the above-mentioned specificflexible polypropylene homopolymers, even when they are notcross-linked.

Furthermore, the present inventors found that a vulcanized rubber likeolefin polymer having physical properties similar to those of the TPO(partially cross-linked) can be obtained by the use of a specificcatalyst system to control crystallinity of the resultant polymers, evenwhen they are not cross-linked.

The present invention is based on the above findings.

SUMMARY OF THE INVENTION

Accordingly, the first embodiment of the present invention resides in:

(I) a flexible polypropylene comprising:

(X) 10 to 90 weight % of boiling heptane soluble polypropylene having anumber average molecular weight of not less than 25,000 and a molecularweight distribution (Mw/Mn) of not more than 7; and

(Y) 90 to 10 weight % of boiling heptane insoluble polypropylene havinga Melt Index of 0.1 to 4 g/10 min.; and

(II) a flexible polypropylene comprising:

(x) 10 to 90 weight % of boiling heptane soluble polypropylene having anintrinsic viscosity of not less than 1.2 dl/g; and

(y) 90 to 10 weight % of boiling heptane insoluble polypropylene havingan intrinsic viscosity of 0.5 to 9.0 dl/g.

The second embodiment of the present invention resides in a propylenebased elastomer composition which comprises:

(o) 10 to 95 weight % of a polypropylene based polymer comprising 10 to90 weight % of boiling heptane soluble polypropylene having an intrinsicviscosity of not less than 1.2 dl/g and 90 to 10 weight % of boilingheptane insoluble polypropylene having an intrinsic viscosity of 0.5 to9.0 dl/g; and 90 to 5 weight % of

(p) an ethylene/propylene copolymer having an ethylene unit content of10 to 60 mol % and an intrinsic viscosity of 0.5 to 7.0 dl/g, or

(p') an ethylene/propylene/polyene copolymer having an ethylene unitcontent of 10 to 60 mol %, a polyene unit content of 1 to 10 mol %, andan intrinsic viscosity of 0.5 to 7.0 dl/g.

The third embodiment of the present invention resides in a non-solventpolymerization process for producing an olefin polymer, which employs acatalyst system comprising:

(A) a solid component composed of (a) crystalline polyolefin and (b) asolid catalyst component consisting of magnesium, titanium, a halogenatom and an electron donor;

(B) an organoaluminum compound;

(C) an alkoxy group-containing aromatic compound represented by thegeneral formula: ##STR1## wherein R¹ is a C₁₋₂₀ alkyl group; R² is aC₁₋₁₀ hydrocarbon group, a hydroxyl group or a nitro group; m is aninteger of 1 to 6; and n is 0 or an integer of 1 to (6-m); and

(D) an electron donative compound.

In addition, an elastomeric polypropylene similar to the atacticpolypropylene of the first embodiment is disclosed in Kokai 54-40889.However, the elastomeric polypropylene can only be produced by using anextremely unique catalyst having insufficient properties, although thethe atactic polypropylene can be produced by using a conventionalindustrial catalyst for polypropylene.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart showing one embodiment of a process for producingatactic polypropylene used as Component (X) of the flexiblepolypropylene of the present invention; and

FIGS. 2 and 3 are flowcharts showing a different embodiment of a processfor producing the flexible polypropylene resin of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described below in more detail.

It is important that, for use in bumpers or sheets as thermoplasticelastomer, the flexible polypropylene resin (I) according to the firstembodiment of the present invention should have an elongation at break(T_(B)) of 400% or more, preferably 500 to 700%; a remaining elongationafter 100% elongation (PS₁₀₀) of 80% or less, preferably 50 to 75%; anda ratio (M_(B) /M_(Y)) of fracture stress (M_(B)) to yield stress(M_(Y)) of 1.0 or more, preferably 1.5 to 3.5. If these dynamicproperties are outside of the above ranges, the objects of the presentinvention cannot be sufficiently achieved.

In the resin (I), the atactic polypropylene used as Component (X) shouldbe one soluble to boiling heptane, having a number average molecularweight (Mn) of at least 25,000, preferably 30,000 to 60,000, and havinga molecular weight distribution (Mw/Mn) of not more than 7, preferably 2to 6. If the atactic polypropylene has a Mn of less than 25,000 or aMw/Mn of more than 7, such atactic polypropylene cannot give improvementof dynamic properties caused by addition of atactic polypropylene to theresultant resin, resulting in low fracture stress (M_(B))/yield stress(M_(Y)) ratio (e.g., less than 1.0) and more remaining elongation after100% elongation (PS₁₀₀) (e.g., more than 80%). In this case, the objectsof the present invention cannot be achieved.

The atactic polypropylene used as Component (X) may be a propylenehomopolymer or a propylene copolymer having a propylene unit and notmore than 40 wt. %, preferably not more than 30 wt. % of the otheralpha-olefin having 2 to 30 carbon atoms. The atactic polypropylene canbe used alone or in combination.

The atactic polypropylene, Component (X) can be produced by a knownmethod as disclosed in, for example Kokai 63-243106. For example,desired atactic polypropylene can be obtained by polymerizing propylenein the presence of a catalyst comprising:

(1) a solid catalyst component containing, as essential components,magnesium, titanium, a halogen atom and an electron donor; (2) anorganoaluminum compound; and (3) an alkoxy group-containing aromaticcompound represented by the general formula: ##STR2## wherein R¹ is aC₁₋₂₀ alkyl group; R² is a C₁₋₁₀ hydrocarbon group, a hydroxyl group ora nitro group; m is an integer of 1 to 6; and n is 0 or an integer of 1to (6-m). FIG. 1 shows one embodiment of a process for producing atacticpolypropylene used as Component (X) of the flexible polypropylene of thepresent invention.

In addition, the ingredients for preparation of the catalyst accordingto the third embodiment of the present invention can be used to preparethe above catalyst.

With respect to the amount of each catalytic component, in general,Component (1) may be used in an amount to provide 0.0005 to 1 mmol per 1liter of a reaction volume in terms of Ti atom. Component (2) may beused in an amount to provide a Component (2) to Ti mol ratio of 1 to3,000, preferably 40 to 800. Component (3) may be used in an amount toprovide a Component (3) to Ti mol ratio of 0.01 to 500, preferably 1 to300.

In the process for producing the atactic polypropylene, theabove-mentioned catalytic components may be added to a reaction system,and then propylene may be introduced into the reaction system. It isalso possible to produce the atactic polypropylene by first blending andcontacting the above Components (1), (2) and (3) in a desired amount,and, immediately after that, introducing propylene into the system toinitiate polymerization. In this case, it is better to age the catalystfor 0.2 to 3 hours after the contact before introducing propylene.

Polymerization methods are not particularly limited, and can be carriedout by any known methods such as a solution polymerization method, asuspension polymerization method and a gas phase polymerization method.The polymerization can be carried out batchwise or continuously. Fromthe view point of efficiency and quality, the solution polymerizationmethod and the suspension polymerization method are particularlypreferred.

As for the reaction conditions for the polymerization reaction, thepropylene pressure may usually range from 1 to 50 Kg/cm² G; and thereaction temperature may usually range from 20 to 200° C., preferablyfrom 60 to 100° C. The molecular weight of the resultant polymer can becontrolled by any known method, for example, a method of controllinghydrogen concentration in a reactor. Usually the reaction time may rangefrom 10 minutes to 10 hours.

Further, propylene as raw material can be used alone or, if desired, incombination with the other alpha-olefins. In this case, it is preferablethat the alpha-olefin be used in amount of not more than 40 wt. %,preferably not more than 30 wt. %, based on the total weight of monomersused. Examples of the other alpha-olefins are C₂₋₃₀ alpha-olefins otherthan propylene, such as ethylene, butene-1, pentene-1, hexene-1,heptene-1, octene-1, nonene-1, decene-1, dodecene-1, tetradecene-1,octadecene-1, 4-methylpenetene-1, 4-methylehexene-1,4,4-dimethylpentene-1 and the like. These alpha-olefins may be usedalone or in combination with two or more kinds.

According to the above process, atactic polypropylene having highmolecular weight and relatively narrow molecular weight distribution canbe produced as Component (X) used in the flexible polypropylene resin(I).

In the resin (I), Component (Y) is boiling heptane insoluble,crystalline isotactic polypropylene having a Melt Index of 0.1 to 4 g/10min. If the MI is less than 0.1 g/10 min., such isotactic polypropylenewill have poor melting properties, resulting in difficulty ininjection-molding. If the MI exceeds 4 g/10 min., such isotacticpolypropylene will have insufficient mechanical properties and thus willnot be suitable as molding material.

The isotactic polypropylene, Component (Y) may be a propylenehomopolymer having isotactic stereoregularity, or a copolymer ofpropylene and the other alpha-olefin having isotactic stereoregularity.The suitable alpha-olefins which can be used in the copolymer may bethose having 2 to 8 carbon atoms such as ethylene, butene-1, pentene-1,hexene-1, heptene-1 and octene-1. Of these, ethylene and butene-1 aremore preferred. The copolymer may be a block copolymer or a randomcopolymer which usually contains not more than 40 wt. %, preferably notmore than 30 wt. % of the other alpha-olefin.

Suitable isotactic polypropylene, Component (Y) includes, for example, apropylene homopolymer and a random or block copolymer of propylene andethylene, having an ethylene unit content of 1 to30 wt. %, preferably 3to 25 wt. %. A process for producing such isotactic polypropylene is notparticularly limited; but can be selected from known methodsconventionally used to produce crystalline polypropylene.

In the flexible polypropylene resin (I) according to the presentinvention, the isotactic polypropylene, Component (Y) can be used aloneor in combination. Further, the atactic polypropylene, Component (X) andthe isotactic polypropylene, Component (Y) may be used to provide aComponent (X) content of 10 to 90 wt. %, preferably 25 to 80 wt. % and aComponent (Y) content of 90 to 10 wt. %, preferably 75 to 20 wt. %. Ifthe content of Component (X) is less than 10 wt. %, the resultant resinhas too big yield stress (M_(Y)), resulting in fracture stress (M_(B))to yield stress (M_(Y)) ratio (M_(B) /M_(Y)) of less than 1.0, and aremaining elongation (PS₁₀₀) after 100% elongation of more than 80%. Inthis case, the objects of the present invention cannot be achieved. Onthe other hand, if the content of Component (X) exceeds 90 wt. %, theresultant resin has poor fracture stress (M_(B)), resulting in M_(B)/M_(Y) ratio of less than 1.0 and lowered mechanical strength. In thiscase, also the objects of the present invention cannot be achieved.

Next, flexible polypropylene resin (II) will be described.

The flexible polypropylene resin (II) contains a boiling heptane solublepolypropylene having an intrinsic viscosity of 1.2 dl/g or more,preferably 1.5 dl/g or more; and a boiling heptane insolublepolypropylene having an intrinsic viscosity of 0.5 to 9.0 dl/g,preferably 1.0 to 6.0 dl/g. It is necessary that the polypropylene resin(II) have a boiling heptane soluble polypropylene content of 10 to 90wt. %, preferably 25 to 70 wt. %; and a boiling heptane insolublepolypropylene content of 90 to 10 wt. %, preferably 75 to 30 wt. %.

If the boiling heptane soluble polypropylene has an intrinsic viscosityof less than 1.2 dl/g, the resultant resin will have poor fracturestress, resulting in loss of rubber elastomeric properties. If theboiling heptane soluble polypropylene content is less than 10 wt. %, theresultant resin may have poor flexibility. If the boiling heptanesoluble polypropylene content is more than 90 wt. %, the resultant resinwill have a tendency to have insufficient mechanical properties.

On the other hand, if the boiling heptane insoluble polypropylene has anintrinsic viscosity of less than 0.5 dl/g, the resultant resin will haveextremely poor impact strength. If the boiling heptane insolublepolypropylene has an intrinsic viscosity of more than 9.0 dl/g, theresultant resin will have a tendency to have difficulty in molding. Inaddition, the intrinsic viscosity should be value measured in a decalinesolution at 135° C.

The flexible polypropylene resin (II) according to the present inventionpreferably has a pentad fraction (rrrr/(1-mmmm)) measured by ¹³ C-NMR,expressed as a percentage of 20% or more; a melting peak temperature(Tm), measured by DSC, of 150° C. or more; and an enthalpy of melting(ΔH) of 100 J/g or less. The resin having a pentad fraction of less than20%, will have poor impact strength at low temperature. The resin havinga melting peak temperature of less than 150° C. will have insufficientheat resistance. The resin having an enthalpy of melting of more than100 J/g will have poor flexibility. In any of these cases, the resultantresin may have insufficient physical properties as thermoplasticelastomer. Further, in the flexible polypropylene resin (II) accordingto the present invention, a domain structure can usually be observed bya transmission type electron microscope.

The flexible polypropylene resin of the present invention may contain,if desired, various additives, reinforcing agents, fillers, such as heatstabilizers, antioxidants, photo stabilizers, antistatic agents,lubricants, nucleating agents, flame retarding agents, pigments, dyes,glass fibers, carbon fibers, calcium carbonate, calcium sulfate, mica,talc and clay. These additives can be added as far as the objects of thepresent invention can be achieved. Further, it is possible to add theother thermoplastic resins, thermoplastic elastomers, rubbers and thelike to the polypropylene resin of the present invention, if desired.

Next, the propylene based elastomer composition according to the secondembodiment of the present invention, will be described.

The composition according to the second embodiment contains 10 to 95 wt.%, preferably 40 to 80 wt. % of a polypropylene based polymer (o), basedon the total weight of the composition. The composition containing lessthan 10 wt. % of the polypropylene based polymer (o), will haveremarkably lowered heat resistance. The composition containing more than95 wt. % of the polymer (o), will have remarkably lowered impactstrength at low temperature.

The polypropylene based polymer (o) is the same as the flexiblepolypropylene resin (II) according to the first embodiment of thepresent invention. The favorable physical properties of thepolypropylene based polymer (o) are the same as those of thepolypropylene resin (II).

The composition according to the second embodiment of the presentinvention has 5 to 90 wt. %, preferably 20 to 60 wt. % of anethylene/propylene copolymer (p) or an ethylene/propylene/dienecopolymer (p') based on the total amount of the composition. Each of thecopolymers (p) and (p') has an ethylene unit content of 10 to 60 mol %,preferably 20 to 50 mol %. If the ethylene unit content is less than 10mol %, the resultant composition has remarkably poor impact strength atlow temperature. If the ethylene unit content is more than 60 mol %, theresultant composition will have poor surface gloss. The copolymers (p)and (p') have an intrinsic viscosity of 0.5 to 7.0, preferably 1.0 to3.0 dl/g. If the intrinsic viscosity is less than 0.5 dl/g, theresultant composition will have remarkably lowered impact strength atlow temperature. If the intrinsic viscosity exceeds 7.0 dl/g, theresultant composition will have poor surface gloss and poor surfaceimpact strength.

The elastomer composition according to the the second embodiment of thepresent invention which consists of the polypropylene based polymer (o)and the copolymer (p) or (p'), preferably has an elongation at break of300% or more, preferably 400% or more; a fracture stress of 100 Kg/cm²or more, preferably 150 Kg/cm² or more; and a tensile elasity of 8000Kg/cm² or less, preferably 5000 Kg/cm² or less.

The elastomer compositions having an elongation at break of less than300% or a fracture stress of less than 100 Kg/cm², are not preferablesince they do not have rubber elastomeric properties. The elastomercompositions having a tensile elasity of more than 8000 Kg/cm² are notpreferable since they do not have low hardness.

Next, a process for producing a olefin polymer according to the thirdembodiment of the present invention, will be described.

Firstly, a catalyst system will be described.

In the catalyst system according to the third embodiment of the presentinvention, a solid component (A) comprises crystalline polyolefin (A-a);and solid catalyst component (A-b) containing magnesium, titanium, ahalogen atom and an electron donor.

The preparation methods of the solid component (A) include, for example:

(1) a method comprising pre-polymerizing an olefin in the presence of amixture of the solid catalyst component (A-b), an organoaluminumcompound and an electron donative compound to be used when desired(Pre-Polymerization Method);

(2) a method which comprises dispersing the solid catalyst component(A-b), an organoaluminum compound and an electron donative compound(melting point: 100° C. or more) which are used when desired, in acrystalline powder such as crystalline polypropylene and polyethylenehaving an uniformed particle size (Dispersion Method); and

(3) A method combining the method (1) and the method (2).

The crystalline polyolefin (A-a) used in the solid component (A)include, for example, crystalline polyolefins obtained fromalpha-olefins having 2 to 10 carbon atoms, such as polyethylene,polypropylene, polybutene, and poly-4-methylpentene. The crystallinepolyolefin (A-a) can be prepared by pre-polymerization as indicated inthe method (1). That is, alpha-olefins having 2 to 10 carbon atoms maybe subjected to pre-polymerization usually at 30 to 80° C., preferablyat 55 to 70° C.

In this case, an aluminum to titanium atomic ratio in the catalystsystem may be usually selected from a range of 0.1 to 100, preferably0.5 to 5; and an electron donor to titanium molar ratio may be selectedfrom a range of 0 to 50, preferably 0.1 to 2. In addition, ascrystalline polyolfin (A-a), the crystalline polyolefin powders soproduced by the preparation method (2) can be used.

In addition, the crystalline polyolefins suitably have a melting pointof 100° C. or more.

The organoaluminum compound which can be used to prepare the solidcomponent (A), may be selected from those for the component (B)described later. Further, the electron donative compounds to be usedwhen desired, may be selected from those for the component (D) describedlater.

The solid catalyst component (A-b) used to prepare the solid component(A) should contain magnesium, titanium, a halogen atom and an electrondonor as essential components. The solid catalyst component (A-b) can beprepared by contacting a magnesium compound, a titanium compound and anelectron donor. In this case, a halogen atom may be contained in themagnesium compound and/or the titanium compound as halogenated compound.

Examples of the magnesium compounds include magnesium dihalides suchas-magnesium dichloride; magnesium alkoxides such as magnesium oxide,magnesium hydroxide, hydrotalcite, salts of carboxylic acids ofmagnesium and magnesium diethoxide; aryloxymagnesium; alkoxymagnesiumhalide; aryloxymagnesium halide; alkylmagnesium such asethylbutylmagnesium; alkylmagnesium halide; and a reaction product of anorganomagnesium compound and an electron donor, halosilane,alkoxysilane, silanol or an aluminum compound. Of these compounds,magnesium halides, alkoxymagnesium, alkylmagnesium, alkylmagnesiumhalides are preferred. In addition, these magnesium compounds can beused alone or in combination.

As the magnesium compounds, a reaction product of metallic magnesium,alcohol and halogen can be used. The metallic magnesium can be in anyform, such as granule, ribbon and powders. Also, the metallic magnesiumshould preferably be free of magnesium oxide film covering it, althoughno specific restrictions are placed on its surface state.

The alcohol is not specifically limited; but it should preferably be alower alcohol having 1 to 6 carbon atoms. Ethanol is most desirable,because it gives a solid catalyst component which greatly improves thecatalyst performance. The alcohol may have any purity and water contentwhich are not specifically limited. It is desirable, however, that thewater content should be 1% or lower, preferably 2000 ppm or lower,because excess water in the alcohol forms magnesium hydroxide on thesurface of metallic magnesium. Moreover, the water content shouldpreferably be as low as possible, usually 200 ppm or lower. Further,suitable halogen includes bromine and iodine. The halogen may be used inany form and state. For example, it may be used in the form of solutionin an alcohol.

The amount of the alcohol usually ranges from 2 to 100 mol, preferablyfrom 5 to 50 mol, per 1 mol of the metallic magnesium. An excess amountof alcohol is likely to give the magnesium compound having poormorphology. With too small an amount of alcohol, it is difficult tocarry out smooth stirring in the reaction vessel. The halogen should beused in an amount of at least 0.0001 gram-atom, preferably at least0.0005 gram-atom, most preferably at least 0.001 gram-atom, per 1 mol ofthe metallic magnesium. With an amount less than 0.0001 gram-atom,without grinding, the magnesium compound is poor in titanium-supportingcapacity, stereoregularity, and morphology. In this case, grinding ofthe magnesium compound is required; however, this is an additional stepand not preferable. The amount of the halogen has no upper limit so longas the desired magnesium compound is obtained. It is possible to controlthe particle size of the resulting magnesium compound by appropriatelyselecting the amount of halogen used.

The reaction of metallic magnesium, alcohol, and halogen may be carriedout by any known method. For example, the reaction may be carried outunder reflux conditions for usually 2 to 30 hours until the reactionsystem does not evolve hydrogen gas any longer, to obtain a desiredmagnesium compound. More specifically, such known methods using iodineas halogen include:

(1) A method which comprises adding iodine in solid form to a mixture ofalcohol and metallic magnesium, and reacting them under refluxing byheating;

(2) A method which comprises adding an alcohol solution of iodinedropwise to a mixture of alcohol and metallic magnesium, and reactingthem under refluxing by heating; and

(3) A method which comprises adding an alcohol solution of iodinedropwise to a mixture of alcohol and metallic magnesium while heatingthe mixture.

Regardless of the method selected, the reaction should preferably becarried out in an inert gas atmosphere such as nitrogen and argon and,if necessary, in the presence of an inert organic solvent such assaturated hydrocarbons such as n-hexane. It is not necessary to placethe metallic magnesium, alcohol, and halogen all at once in the reactionvessel. It is possible to place them by portions in the reaction vessel.For example, it is possible to place all of the alcohol in the reactionvessel at the beginning and then to add metallic magnesium by portionsseveral times. This procedure prevents the reaction system from evolvinghydrogen gas in a large amount at one time and hence ensures safety andpermits the use of a smaller reaction vessel, without the partial lossof alcohol and halogen by splashing. The number of portions should beproperly determined according to the size of the reaction vessel; but itis usually 5 to 10 to avoid unnecessary complexity.

The reaction may be carried out batchwise or continuously. There is amodified method which comprises repeating the steps of adding a smallportion of metallic magnesium to as much alcohol as necessary placed ina reaction vessel and removing the reaction product.

The obtained magnesium compound can be used as such in the next stepwithout necessity for grinding or classification for a desired particlesize distribution.

The titanium compounds include, for example, titanium tetraalkoxidessuch as titanium tetramethoxide, titanium tetraethoxide, titaniumtetra-n-propoxide, titanium tetraisopropoxide, titaniumtetra-n-butoxide, titanium tetraisobutoxide, titanium tetrahexyloxideand titanium tetraphenoxide; titanium tetrahalides such as titaniumtetrachloride, titanium tetrabromide and titanium tetraiodide;alkoxytitanium trihalides such as methoxytitanium trichloride,ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride and ethoxytitanium tribromide;dialkoxytitanium dihalides such as dimethoxytitanium dichloride,diethoxytitanium dichloride, dipropoxytitanium dichloride,di-n-propoxytitanium dichloride and diethoxytitanium dibromide; andtrialkoxytitanium monohalides such as trimethoxytitanium chloride,triethoxytitanium chloride, tripropoxytitanium chloride andtri-n-butoxytitanium chloride. Of these, preferred are higherhalogenated titanium compound, particularly titanium tetrachloride.These titanium compounds can be used alone or in combination.

Further, the halogen atoms include a fluorine atom, chlorine atom,bromine atom and iodine atom. These halogen atoms are usually containedin the magnesium compounds and/or the titanium compounds.

In addition, as electron donors, those which will be described later forcomponent (D) can be used.

The above solid catalyst component (A-b) can be prepared by any knownprocesses as described in, for example, Kokai 53-43094; 55-135102;55-135103; and 56-18606. The known processes include:

(1) a process comprising grinding a magnesium compound or a complex of amagnesium compound and an electron donor compound in the presence of anelectron donor compound and, if desired, a grinding promoter, and thenreacting the ground mixture with halogenated titanium;

(2) a process comprising reacting a magnesium compound in the form ofliquid, having no reduction capability, with liquid halogenated titaniumin the presence of an electron donor compound to precipitate a titaniumcomplex in a solid form;

(3) a process comprising further reacting the resultant product ofProcess (1) or (2) with halogenated titanium;

(4) a process comprising further reacting the resultant product ofProcess (1) or (2) with an electron donor compound and halogenatedtitanium;

(5) a process comprising grinding a magnesium compound or a complex of amagnesium compound and an electron donor compound in the presence of anelectron donor compound, a titanium compound and, as desired, a grindingpromoter, and then treating the ground mixture with halogen or a halogencompound;

(6) a process comprising treating the compounds obtained in any one ofProcess (1) to (4) with halogen or a halogenated compound.

Further, the solid catalyst component (A-b) can be prepared by processother than those mentioned above, for example, those described in Kokai56-166205; 57-63309; 57-190004; 57-300407; and 58-47003.

In addition,, the solid catalyst component (A-b) can be prepared by aprocess which comprises contacting an oxide of elements belonging to theII to IV Groups of the Periodic Table (such as silicon oxide, magnesiumoxide and aluminum oxide), or oxide complex containing at least oneoxide of elements belonging to the II to IV Groups of the Periodic Table(such as a solid product wherein the above magnesium compound is carriedon silica-alumina), with an electron donor compound and halogenatedtitanium in a solvent at 0 to 200° C., preferably 10 to 150° C. for 2minutes to 24 hours.

The preparation of the solid catalyst component (A-b) can be carried outin a solvent inert to the magnesium compound, the electron donorcompound and the halogenated titanium. Such inert solvents includealiphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbonssuch as benzene and toluene; halogenated hydrocarbons such as mono- andpolyhalogen compounds of fatty, cyclic or aromatic hydrocarbons, whichmay be saturated or unsaturated, having 1-12 carbon atoms.

In general, the thus prepared solid catalyst compound (A-b) has amagnesium to titanium atomic ratio of 2 to 100; a halogen to titaniumatomic ratio of 5 to 200 and an electron donor to titanium molar ratioof 0.1 to 10.

In the above solid component (A), the ratio of the crystallinepolyolefin (A-a) and the solid catalyst component (A-b) is such that acomponent (A-b)/component (A-a) ratio generally ranges from 0.033 to200, preferably from 0.10 to 50.

The organoaluminum compounds (B) which can be used in the catalystsystem used in the third embodiment of the present invention, arerepresented by the following formula:

    AlR.sup.3.sub.p X.sub.3-p

wherein R³ is an alkyl group having 1-10 carbon atoms; and X is ahalogen atom such as chlorine or bromine; and p is an integer of 1 to 3.Examples of the aluminum compound include trialkylaluminum such astrimethylaluminum, triethylaluminum, triisopropylaluminum,triisobutylaluminum and trioctylaluminum; and dialkylaluminum monohalidesuch as diethylaluminum monochloride, diisopropylaluminum monochloride,diisobutylaluminum monochloride and dioctylaluminum monochloride; andalkylaluminum sesquihalide such as ethylaluminum sesquichloride. Theseorganoaluminum compounds may me used alone or in combination.

The alkoxy group-containing aromatic compounds (C), which are used inthe catalyst system of the third embodiment of the present invention,are represented by the general formula: ##STR3## wherein R¹ is an alkylgroup having 1 to 20 carbon atoms; R² is a hydrocarbon having 1 to 10carbon atoms, hydroxyl group or nitro group; m is an integer of 1 to 6;and n is an integer of 0 to (6-m). The aromatic compounds (C) include,for example, monoalkoxy compounds such as m-methoxytoluene,o-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol,vinylanisole, p-(1-propenyl)anisole, p-allylanisole,1,3-bis(p-methoxyphenyl)-1-pentene, 5-allyl-2-methoxyphenol,4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzylalcohol,methoxybenzylalcohol, nitroanisole and nitrophenetole; dialkoxycompounds such as o-dimethoxybenzene, m-dimethoxybenzene,p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6-dimethoxyphenol and1-allyl-3,4-dimethoxybenzene; trialkoxy compounds such as1,3,5-trimethoxybenzene, 5-allyl-1,2,3-trimethoxybenzene,5-allyl-1,2,4-trimethoxybenzene, 1,2,3-trimethoxy-5-(1-propenyl)benzene,1,2,4-trimethoxy-5-(1-propenyl)benzene, 1,2,3-trimethoxybenzene and1,2,4-trimethoxybenzene. Of these, preferred are dialkoxy compounds andtrialkoxy compounds. These alkoxy group-containing compounds can be usedalone or in combination.

The electron donor compounds (D) used in the catalyst system of thethird embodiment of the present invention, are compounds containingoxygen, nitrogen, phosphorus, sulfur, silicon and the like. Basically,the compounds that can improve stereoregurality in propylenepolymerization are considered to be useful.

The electron donor compounds (c) include, for example, organosiliconcompounds, esters, thioester, amines, ketones, nitriles, phosphines,etheres, thioethers, acid anhydrides, acid halides, acid amides,aldehydes and organic acids.

Further, the electron donor compounds include, for example,organosilicon compounds such as diphenyldimethoxysilane,diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane,tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane,methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane and benzyltrimethoxysilane; esters of aromatcidicarboxylic acid such as n-butylphthalate and diisobutylphthalate; C₁₋₄alkyl esters of aromatic monocarboxylic acids such as benzoic acid,p-methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid;non-symmetric ethers such as isopropyl methyl ether, isopropyl ethylether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl n-propylether, t-butyl n-butyl ether, t-amyl methyl ether and t-amyl ethylether; azo compounds where a steric hindrance substituent is bonded toan azo bond, such as 2,2'-azobis(2-methylpropane),2,2'-azobis(2-ethylpropane), 2,2'-azobis(2-methylpentane),alpha,alpha'-azobisisobutylonitrile, 1,1'-azobis(1-cyclohexanecarboxylicacid), (1-phenylmethyl)-azodiphenylmethane and1-phenylazo-2,4-dimethyl-4-trixypentanenitrile. These compounds can beused alone or in combination.

More specifically, the electron donor compounds include, for example,di-esters of aromatic dicarboxylic acids such as diethyl phthalate,diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, methylethyl phthalate, methylpropyl phthalate, methyl isobutyl phthalate,ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutylphthalate, dimethyl terephthalate, diethyl terephthalate, dipropylterephthalate, diisobutyl terephthalate, methyl ethyl terephthalate,methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propylterephthalate, ethyl isobutyl terephthalate, propyl isobutylterephthalate, dimethyl isophthalate, diethyl isophthalate, dipropylisophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methylpropyl isophthalate, methyl isobutyl isophthalate, ethyl propylisophthalate, ethyl isobutyl isophthalate and propyl isobutylisophthalate;

mono-esters such as methyl formate, ethyl acetate, vinyl acetate, propylacetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethylacetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate,methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate,ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butylbenzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzylbenzoate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, ethylanisate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethylnaphthoate; esters having 2 to 18 carbon atoms such asgamma-valerolactone, coumarin, phthalide and ethylene carbonate;

aromatic carboxylic acids such as benzoic acid and p-oxybenoic acid;

acid anhydrides such as succinic acid anhydride, benzoic acid anhydrideand p-toluic acid anhydride;

ketones having 3-15 carbon atoms such as acetone, methyl ethyl ketone,methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone;

aldehydes having 2-15 carbon atoms such as acetaldehyde, octyl aldehyde,benzaldehyde, tolualdehyde and naphthaldehyde;

acid halides having 2-15 carbon atoms such as acetyl chloride, benzylchloride, toluic acid chloride and anisic acid chloride;

ethers having 2-20 carbon atoms such as methyl ether, ethyl ether,isopropyl ether, ter.-butyl methyl ether, ter.-butyl ethyl ether,n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether,ethylene glycol butyl ether;

acid amides such as acetic acid amide, benzoic acid amide and toluicacid amide;

amines such as tributyl amine, N,N'-dimethylpiperazine,2,2,6,6-tetramethylpiperidine, tribenzylamine, aniline, pyridine,pycoline and tetramethyl ethylene diamine; and

nitriles such as acetonitrile, benzonitrile, tolunitrile.

Of these compounds, preferred are organosilicon compounds, esters,ethers, ketones and acid anhydrides. Particularly preferred areorganosilicon compounds such as diphenyldimethoxysilane andphenyltriethoxysilane; di-esters of aromatic dicarboxylic acids such asdi-n-butyl phthalate and diisobutyl phthalate; and C₁₋₄ alkyl esters ofaromatic monocarboxylic acid such as benzoic acid, p-methoxybenzoicacid, p-ethoxybenzoic acid and toluic acid. The di-esters of aromaticdicarboxylic acids are particularly preferred since they can improve acatalytic activity and activity durability.

In the third embodiment of the present invention, each component of thecatalyst is used in the following amounts. The solid catalyst component(A) may be used in an amount of from 0.0005 to 1 mmol per 1 liter of areaction volume, in terms of titanium atom. The organoaluminum compound,Component (B), may preferably be used in an amount to provide an Al/Tiatomic ratio of 1 to 3000, more preferably from 40 to 800. The use ofthe ranges outside of the atomic ratio will result in poor catalyticactivity. The alkoxy group-containing aromatic compound may preferablybe used in an amount to provide an aromatic compound/titanium molarratio of 0.1 to 500, more preferably 1 to 300. The use of the molarratio less than 0.1 will result in poor physical properties of theresultant polymers. The molar ratio more than 500 may result in poorcatalytic activity. The electron donor compounds (D) may be used in anamount to provide a compound (C)/compound (D) molar ratio of usually0.01 to 100, preferably 0.2 to 100.

The process for the production of olefin polymers using theabove-mentioned catalyst system of the present invention will bedescribed below.

In the embodiment of the present invention, at least one alpha-olefin ispolymerized in the presence of the above-mentioned catalyst system, toproduce alpha-olefin homopolymers such as propylene homopolymer oralpha-olefin copolymers such as propylene/alpha-olefin random copolymersand ethylene/propylene block copolymers.

Examples of the alpha-olefins used as starting materials are thosehaving 2 to 30 carbon atoms, such as ethylene, propylene, butene-1,pentene-1, 4-methylpentene-1, heptene-1, nonene-1 and decene-1. Theseolefins can be used alone or in combination.

As to the type of polymerization, a non-solvent polymerization methodsuch as gas phase polymerization or bulk polymerization can be used. Thegas phase polymerization is preferably used.

The gas phase polymerization includes a gas phase one-steppolymerization method where the polymerization is carried out in onestep; and a gas phase multi-step polymerization method. The gas phaseone-step method is used to produce alpha-olefin homopolymers such aspropylene homopolymers, propylene/alpha-olefin random copolymers, andthe like. The gas phase multi-step method is used to produceethylene/propylene block copolymers, ethylene/propylene/polyene blockterpolymers, and the like.

The reaction conditions for the gas phase one-step polymerization methodare such that the polymerization pressure may usually range from 10 to45 Kg/cm².G, preferably 20 to 30 Kg/cm².G, and the polymerizationtemperature may usually range from 40 to 90° C., more preferably 60 to75° C. The molecular weight of the resultant polymer can be controlledby any known methods, for example, a method of controlling hydrogenconcentration in a reactor. The reaction time may vary depending uponkinds of olefins, reaction temperature and the like, and cannot bereadily specified. Usually the reaction time may range from 5 minutes to10 hours.

In the case of polymerization by the gas phase one-step method, suitablealpha-olefins as starting materials are propylene for production ofhomopolymers; propylene and C₄₋₃₀ alpha-olefins for production ofcopolymers. In the case of copolymerization, a propylene/alpha-olefinmolar ratio is preferably 0.2 to 20.

In the case of polymerization by the gas phase multi-step polymerizationmethod, the first polymerization may be homopolymerization orcopolymerization of alpha-olefins (preferably homopolymerization ofpropylene or copolymerization of propylene and C₄₋₃₀ alpha-olefins). Themolecular weight control can be made by a known method such as hydrogengas concentration control. The polymerization temperature may usuallyrange from 40 to 90° C., more preferably 60 to 75° C. The polymerizationpressure may usually range from 10 to 45 Kg/cm².G, preferably 20 to 30Kg/cm².G. The reaction time may range from 5 minutes to 10 hours.

The second to final (n-step) polymerization may be copolymerization ofethylene/propylene or ethylene/propylene/polyene.

Suitable polyenes include, for example, non-conjugated polyenes such asdicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene,5-methylene-2-norbornene, 5-ethylidene-2-norbornene,5-isopyridene-2-norbornene, 5-isopropenyl-2-norbornene,5-(1-butenine)-2-norbornene, cyclooctadiene, vinylcyclohexane,1,5,9-cyclododecatoriene, 6-methyl-4,7,8,9-tetrahydroindene,2,2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene,4-methyl-1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene,1,4,7-octadiene, 5-methyl-1,8-nonadiene, norbornadiene andvinylnorbornene. Of these non-conjugated polyenes, particularlypreferred are dicyclopentadiene, 5-ethylidene-2-norbornene and1,7-octadiene.

In each polymerization step, molecular weight control can be made by aknown method such as hydrogen gas concentration control. In the case ofan ethylene/propylene copolymer, the control of ethylene unit contentcan be made by controlling a gas ratio of gas used. In the case ofethylene/propylene/polyene copolymers, the control of the polyene unitcontent can be made by controlling the amount of the polyene compoundsused. The polymerization temperature may usually range from 20 to 90°C., more preferably 40 to 50° C. The polymerization pressure may usuallyrange from 5 to 30 Kg/cm².G, preferably 10 to 20 Kg/cm².G. The reactiontime may range from 5 minutes to 10 hours.

In addition, according to the above gas phase multi-step polymerizationmethod, and ethylene/propylene block copolymer, andethylene/propylene/polyene block terpolymer and the like can beproduced.

In the above-mentioned polymerization, immediately after components (A)to (D) are mixed at a prescribed ratio and contacted with each other, anolefin may be introduced to initiate the polymerization. To age thecatalyst components, it is possible to introduce olefin into a reactor,0.2 to 3 hours after such contact of catalyst components. Further, it ispossible to supply the catalyst components suspended in an inert solventor an olefin.

In the third embodiment of the present invention, post treatment afterpolymerization can be conducted by any known methods. In the case of agas phase polymerization, the resultant polymer powders supplied from apolymerization reactor may be treated with nitrogen stream to removeolefins contained in the polymer powders. If desired, the resultantpolymer powders may be pelletized. During the pelletization, a smallamount of water, alcohol or the like may be added to the powders inorder to completely inactivate the catalyst. Further, in the case ofbulk polymerization, after polymerization, remaining monomers may beremoved completely from the resultant polymer and then the polymer maybe pelletized.

There will be described a process for producing the flexiblepolypropylene resin of the first embodiment of the present invention andthe propylene based elastomer of the second embodiment of the presentinvention.

More specifically, the flexible polypropylene resin can be produced bythe following gas phase one-step polymerization method, and thepropylene based elastomer can be produced by the following gas phasetwo-step method with good results.

Further, the flexible polypropylene resin can be produced by thefollowing slurry one-step polymerization method or blending method (I).The propylene based elastomer can be produced by the following slurrymulti-step polymerization method or blending method (II).

GAS PHASE ONE-STEP POLYMERIZATION METHOD

In a gas phase one-step method, propylene monomers are polymerized inthe presence of the catalyst according to the above third embodiment ofthe present invention, to produce a desired flexible polypropyleneresin. In this case, suitable polymerization conditions and a molecularweight weight control method are as described before for the thirdembodiment of the present invention.

FIG. 2 is a flowchart showing one example of a process for production ofthe flexible polypropylene resin of the present invention, using a gasphase one-step method.

GAS PHASE MULTI-STEP POLYMERIZATION METHOD

In a gas phase multi-step method, the catalyst according to the thirdembodiment of the present invention, and the like can be used.

In the gas phase multi-step method, the first polymerization (first steppolymerization) is production of propylene homopolymers.

The second to final (n-step) polymerization is copolymerization ofethylene/propylene or copolymerization of ethylene/propylene/polyene.

Examples of the non-conjugated polyene which can be used herein toproduce the copolymers, are those described in the above description ofthe third embodiment.

Further, suitable polymerization conditions and molecular weight controlare as described in the description of the third embodiment.

SLURRY ONE-STEP GAS POLYMERIZATION METHOD

In a slurry one-step method, for example, any one of the followingcatalysts (1) and (2) can be used.

(1) a catalyst system comprising (i) a solid catalyst componentcontaining, as essential components, magnesium, titanium, a halogen atomand an electron donor, (ii) an alkoxy group-containing aromaticcompound; and (iii) an organoaluminum compound.

(2) a catalyst system comprising (a) a solid compound prepared byreacting (i) the above solid catalyst component and (ii) an alkoxygroup-containing aromatic compound in the presence or absence of (iii)an organoaluminum compound; and (b) an organoaluminum compound.

First, the catalyst system (1) will be described. The solid catalystcomponent (i) comprises, as essential components, magnesium, titanium, ahalogen atom and an electron donor, and can be prepared by contacting amagnesium compound, a titanium compound and an electron donor.

In the preparation of the solid catalyst component (i), solvents can beused, which include a solvent inert to the magnesium compound, theelectron donor and the titanium compound, such as aliphatic hydrocarbonssuch as hexane and heptane; aromatic hydrocarbons such as benzene andtoluene; halogenated hydrocarbons such as mono- and polyhalogenatedcompounds of fatty, cyclic or aromatic hydrocarbons, which may besaturated or unsaturated, having 1 to 12 carbon atoms. These solventscan be used alone or in combination.

The magnesium compounds, titanium compounds and electron donativecompounds for use in preparing the solid catalyst compound (i) of thecatalyst system (1) can be the same as those described for the thirdembodiment of the present invention. The solid catalyst component (i)can be prepared from these compounds by any known methods such as a gasphase multi-step method.

The alkoxy group-containing aromatic compound (ii) and theorganoaluminum compound (iii) to be contacted with the thus obtainedsolid catalyst component (i), can be the same as those described for thethird embodiment of the present invention.

Each component of the catalyst system (1) is used in the followingamounts. The solid catalyst component (i) may be used in an amount offrom 0.0005 to 1 mmol per 1 liter of a reaction volume, in terms oftitanium atom. The alkoxy group-containing aromatic compound (ii) maypreferably be used in an amount to provide an aromatic compound/titaniummolar ratio of 0.1 to 500, more preferably 1 to 300. The use of themolar ratio less than 0.01 will result in poor physical properties ofthe resultant polymers. The molar ratio more than 500 may result in poorcatalytic activity. The organoaluminum compound (iii) may preferably beused in an amount to provide an Al/Ti atomic ratio of 1 to 3000, morepreferably from 40 to 800. The use of the ranges outside of the atomicratio will result in poor catalytic activity.

Next, the catalyst system (2) will be described. The solid component (a)of the catalyst system (2) can be prepared by reacting the solidcomponent (i) of the above catalyst system (1) and the alkoxygroup-containing aromatic compound (ii) in the presence or absence ofthe above-mentioned organoaluminum compound (iii). In the preparation, ahydrocarbon solvent (e.g., hydrocarbon solvents used to prepare theabove catalyst system (1)), can usually be used.

The reaction temperature may usually range from 0 to 150° C., preferably10 to 50° C. If the temperature is less than 0° C., the reaction cannotprogress sufficiently. If the temperature is more than 150° C., a sidereaction may occur, resulting in poor activity.

The reaction time may vary depending upon the reaction temperature, andmay usually range from 1 minute to 20 hours, preferably from 10 to 60minutes.

In the case of preparing the-solid component (a) in the presence of theorganoaluminum compound (III), the concentration of the aluminumcompound (iii) may usually be from 0.05 to 100 mmol/l, preferably from 1to 10 mmol/l. If the concentration is less than 0.05 mmol/l, theadvantages of the organoaluminum compound (iii) cannot be sufficientlyobtained. If the concentration is over 100 mmol/l, the reduction oftitanium in the solid catalyst component will proceed, resulting in pooractivity.

On the other hand, in the case of preparing the solid component byreacting the solid catalyst component (i) and the alkoxygroup-containing aromatic compound (ii) in the absence of theorganoaluminum compound (iii), the alkoxy group-containing compound (ii)is used in an amount to provide a ratio of the compound (ii) to thesolid catalyst component (i) of generally 0.1 to 200, preferably 1 to50. The concentration of the compound (ii) may usually range from 0.01to 10 mmol/l, preferably 0.1 to 2 mmol/l. If the molar ratio in terms oftitanium atom is outside of the above range, it is difficult to obtain acatalyst having a desired activity. If the concentration is less than0.01 mmol/l, the resultant catalyst will have low volume efficiency andwill not be suitable for practical use. If the concentration exceeds 10mmol/l, an extra reaction is likely to occur, resulting in poorcatalytic activity.

The organoaluminum compounds as described for the third embodiment ofthe present invention, can be also used for the organoaluminum compound(b) for the catalyst system (2).

Each component of the catalyst system (2) is used in the followingamounts. The solid catalyst component (a) may be used in an amount offrom 0.0005 to 1 mmol per 1 liter of a reaction volume, in terms oftitanium atom. The organoaluminum compound (b) may preferably be used inan amount to provide an Al/Ti atomic ratio of 1 to 3000, more preferablyfrom 40 to 800. The use of the ranges outside of the atomic ratio willresult in poor catalytic activity.

If the flexible polypropylene polymers are produced using the thusobtained catalyst system (1) or (2), the reaction conditions may bedescribed as follows. The reaction temperature may usually range from 0to 200° C., more preferably 60 to 100° C. The reaction pressure mayusually range from 1 to 50 Kg/cm².G. The reaction time may range from 5minutes to 10 hours. In addition, molecular weight control can be madeby a known method such as hydrogen gas concentration control.

FIG. 3 is a flowchart showing one example of a process for production ofthe flexible polypropylene resin according to the first embodiment ofthe present invention, using a slurry one-step method. In addition, aproduction of the flexible polypropylene resin by a slurry one-stepmethod can be also carried out by a method as shown in the flowchart ofFIG. 1.

SLURRY MULTI-STEP GAS POLYMERIZATION METHOD

The same catalyst system used in the above-mentioned slurry one-steppolymerization method can be used in this multi-step method.

In the slurry multi-step method, the order of polymerization and thenumber of polymerization steps are not particularly limited, and can befreely selected. For example, in the first and third steps ofpolymerization, homopolymerization of propylene can be carried out, andin the second or fourth steps, copolymerization of ethylene/propylenecopolymers and ethylene/propylene/polyene copolymers can be carried out.The number of polymerization steps (n) can be selected as optimum numberto obtain a desired product as is the same case with the above-mentionedgas phase multi-step method. The polymerization can be carried outcontinuously or batchwise.

In the case of production of propylene homopolymers, the polymerizationtemperature may usually range from 0 to 200° C., more preferably 60 to100° C. The propylene pressure may usually range from 1 to 50 Kg/cm².G.In the case of production of an ethylene/propylene copolymer or anethylene/propylene/polyene copolymer, the polymerization temperature mayusually range from 0 to 200° C., preferably 40 to 80° C. The olefinpressure may usually range from 1 to 50 Kg/cm².G.

In the above polymerization, the reaction time may range from 5 minutesto 10 hours. In addition, molecular weight control can be made by aknown method such as hydrogen gas concentration control.

In the case of production of an ethylene/propylene copolymer, theethylene unit content can be controlled by controlling the ratio ofcomponents of the gas used. In the case of production of anethylene/propylene/polyene copolymer, the polyene unit content can becontrolled by controlling the amount of each component used. The polyenemonomers as described for the third embodiment of the present inventioncan be also used herein.

BLENDING METHOD I

The flexible polypropylene resin (I) according to the first embodimentof the present invention, can be prepared by melt-blending, forexample,the above component (X) and component (Y) in a prescribedamount, using a blender such as a kneader, a roll, Banbury mixer or anextruder with one roll bar or two roll bars.

BLENDING METHOD II

The elastomer composition according to the second embodiment of thepresent invention can be prepared by blending a propylene homopolymer(o) and and ethylene/propylene copolymer (p) or anethylene/propylene/polyene copolymer (p') by a known method such asdry-blending or mixing. The propylene homopolymer (o) can be produced bythe above-mentioned gas phase multi-step polymerization method or aslurry multi-step polymerization method. Further, the ethylene/propylenecopolymer (p) and the ethylene/propylene/polyene copolymer (p') can beproduced by a known method, respectively.

EXAMPLES

The present invention will be described in more detail with reference tothe following examples, which are not intended to restrict the scope ofthe invention.

Preparation (1): Preparation of HSP-1 and HIP

(1) Preparation of Solid Catalyst Component

In a 500 ml three-necked glass flask sufficiently purged with nitrogen,were placed 20 ml of purified heptane, 4 g of Mg(OEt)₂ and 1.2 g ofdi-n-butyl phthalate. To the reaction mixture, 5 ml of TiCl₄ was addeddropwise while the temperature of the reaction system was kept at 90° C.110 ml of TiCl₄ was further added and then the reaction mixture washeated to 110° C. for 2 hours. Thereafter, the reaction product waswashed with 100 ml of purified heptane. Then, 115 ml of TiCl₄ was addedto the solid portion of the reaction product, and the reaction wasfurther carried out at 110° C. for 2 hours. After completion of thereaction, the reaction product was washed with 100 ml of purifiedheptane several times to obtain a solid catalyst component.

(2) Polymerization of Propylene

In a 1 liter stainless autoclave, were placed 400 ml of n-heptane, 1.0mmol of triethylaluminum (AlEt₃), 0.025 mmol of1-allyl-3,4-dimethoxybenzene (ADMB) and 6 mg of the solid catalystcomponent obtained in the above procedures. Then, the polymerization wascarried out under a propylene pressure of 8 Kg/cm².G at 70° C. for 2hours. Then, 4 liter of n-heptane per 40 g of the resultant polymer wasadded to the resultant polymer, and the mixture was subjected toheat-refluxing while being stirred with a stirrer for 2 hours. Then, thereaction mixture was subjected to heat filtration, and atacticpolypropylene, HSP-1 was recovered from the filtrate. The HSP-1 had a Mnof 37,000 and a Mw/Mn of 4.7.

On the other hand, the filter cake was recovered to obtain isotacticpolypropylene, HIP. The HIP had a MI of 0.43 g/10 min.

Preparation (2): Preparation of HSP-2 to HSP-4

The same procedures as in Preparation (1) were repeated to prepareatactic polypropylene, HSP-2, HSP-3 and HSP-4 except that the amount ofADMB added was changed.

Preparation (3): Preparation of HSP-7

The same procedures as in Preparation (1) were repeated except that thesolid product prepared by drying the product resulting from thefollowing reaction of metallic magnesium, ethanol and iodine was usedinstead of Mg(OEt)₂.

[Reaction of Metallic Magnesium, Ethanol and Iodine]

A glass reactor (inner Volume: 6 liter) equipped with a stirrer waspurged with nitrogen gas. To the reactor, were introduced 160 g ofmetallic magnesium, about 2430 g of ethanol and 16 g of iodine. Thereaction was carried out under heating and refluxing conditions whilethe reaction mixture was stirred until generation of hydrogen ended toobtain a reaction product.

The polymerization of propylene was carried out in the same manner as inPreparation (1) to prepare atactic polypropylene regarded as HSP-7.

Preparation (4): Preparation of HSP-8

The same procedures as in Preparation (2) were repeated except that thereaction product of metallic magnesium, ethanol and iodine was usedwithout being dried, but filtered.

The polymerization of propylene was carried out in the same manner as inPreparation (2) to prepare atactic polypropylene as HSP-8.

Example 1

As antioxidant, 2000 wt. ppm of 2,6-di-t-butyl-p-cresol (BHT) was addedto a mixture of 50 parts by weight of HSP-1 and 50 parts by weight ofHIP, both prepared in the above Preparation. The obtained mixture wasmelt-blended by a laboplast mil having an inner volume of 30 ml at arevolution of 70 rpm at 195° C. for 2 minutes to obtain a flexiblepolypropylene resin. Thereafter, the physical properties of the pressedarticle of the blended material were measured. The results are as shownin Table 1.

Examples 2 to 4, 8, and 9, and Comparative Examples 3 and 4

The same procedures as in Example 1 were repeated except that the amountof HSP-1 or HIP used was changed. The results are as shown in Table 1.

Comparative Example 1

The same procedures as in Example 1 were repeated except that HSP-5prepared using a catalyst system composed of TiCl₄ /butylbenzoate/MgCl₂and AlEt₃ was used instead of HSP-1. The results are as shown in Table1.

Examples 5 to 7

The same procedures as in Example 1 were repeated except that HSP-2,HSP-3 or HSP4 was used instead of HSP-1. The results are as shown inTable 1.

Comparative Example 2

The same procedures as in Example 1 were repeated except that HSP-6(prepared in the same manner as in the preparation of HSP-1 except thathydrogen was added during polymerization) was used instead of HSP-1. Theresults are as shown in Table 1.

Examples 10 and 11

The same procedures as in Example 1 were repeated except that HSP-7 orHSP-8 was used instead of HSP-1. The results are as shown in Table 1.

                  TABLE 1 (1)                                                     ______________________________________                                        Component                                                                             Component (X)                                                                                       Amount                                                                              Component (Y)                               Kinds Mn Mw/Mn (pbw.) Amount (pbw.)                                         ______________________________________                                        Example 1                                                                             HSP-1    37,000  4.7    50    50                                        Example 2 HSP-1 37,000 4.7 60 40                                              Example 3 HSP-1 37,000 4.7 40 60                                              Example 4 HSP-1 37,000 4.7 75 25                                              Comp. Ex. 1 HSP-5 16,000 8.7 50 50                                            Example 5 HSP-2 32,000 5.3 50 50                                              Example 6 HSP-3 35,000 4.7 50 50                                              Example 7 HSP-4 41,000 4.5 50 50                                              Comp. Ex. 2 HSP-6 19,000 4.5 50 50                                            Example 8 HSP-1 37,000 4.7 25 75                                              Example 9 HSP-1 37,000 4.7 85 15                                              Comp. Ex. 3 HSP-1 37,000 4.7  6 94                                            Comp. Ex. 4 HSP-1 37,000 4.7 97  3                                            Example 10 HSP-7 37,000 4.7 50 50                                             Example 11 HSP-8 37,000 4.7 50 50                                           ______________________________________                                    

                  TABLE 1 (2)                                                     ______________________________________                                        Physical Properties                                                                   TB      MB       MY             PS100                                   (%) (kg/cm.sup.2) (kg/cm.sup.2) MB/MY (%)                                   ______________________________________                                        Example 1                                                                             650     260      100     2.6    70                                      Example 2 670 200  95 2.1 67                                                  Example 3 610 280 120 2.3 72                                                  Example 4 750 145  80 1.8 65                                                  Comp. Ex. 1 800 130 175 0.7 100                                               Example 5 670 240 105 2.3 71                                                  Example 6 600 260 100 2.6 70                                                  Example 7 690 275  95 2.9 69                                                  Comp. Ex. 2 770 145 165 0.9 100                                               Example 8 580 300 180 1.7 76                                                  Example 9 820 120  45 2.7 64                                                  Comp. Ex. 3 330 325 365 0.9 100                                               Comp. Ex. 4 970  70 -- -- 64                                                  Example 10 650 260 100 2.6 70                                                 Example 11 650 260 100 2.7 69                                               ______________________________________                                         Note:                                                                         TB: Elongation at Break                                                       MB: Fracture Stress                                                           MY: Yield Stress                                                              PS100: Romaining Elongation After 100% Elongation                        

Example 12

(1) Preparation of Solid Catalyst Component (A-b)

In a 500 ml three-necked glass flask sufficiently purged with nitrogen,were placed 20 ml of purified heptane, 4 g of Mg(OEt)₂ and 1.2 g ofdi-n-butyl phthalate. To the reaction mixture, 4 ml of TiCl₄ was addeddropwise while the temperature of the reaction system was kept at 90° C.111 ml of TiCl₄ was further added and then the reaction mixture washeated to 110° C. for 2 hours. Thereafter, the reaction product waswashed with 100 ml of purified heptane heated to 80° C. Then, 115 ml ofTiCl₄ was added to the solid portion of the reaction product, and thereaction was further carried out at 110° C. for 2 hours. Aftercompletion of the reaction, the reaction product was washed with 100 mlof purified heptane several times, to obtain a solid catalyst component.

(2) Preparation of Solid Component (A)

In a 2.5 liter three-necked, pressure glass flask sufficiently purgedwith nitrogen, were placed 1.7 liter of purified heptane, 0.07 mol ofAlEt₃, 0.05 mmol of diphenyldimethoxysilane (DPDMS) and 120 g of thesolid catalyst component obtained in the above Preparation (1). Then,the reaction system was kept at 30° C. and under an inner pressure of0.5 g/cm².G by continuously adding propylene while the reaction mixturewas stirred. The reaction was carried out for one hour. Then, thereaction product was purified 5 times with 1 liter of purified heptaneto prepare a solid catalyst component (A).

(3) Gas Phase One-Step Polymerization

To a 5 liter stainless, pressure autoclave, were charged 20 g ofpolypropylene powders, 3 mmol of AlEt₃, 0.15 mmol of1-allyl-3,4-dimethoxybenzene (ADMB), 0.23 mmol ofdiphenyldimethoxysilane (DPDMS) and 20 ml of heptane solution containing100 mg of the solid catalyst component (A) (0.06 mmol: calculated interms of Ti atom). After the reaction system was evacuated for 5minutes, propylene gas was supplied until the total pressure of thereaction system reached 28 Kg/cm². Then, the gas phase polymerizationwas carried out at 70° C. for 17 hours to obtain 640 g of a flexiblepolypropylene resin having a MI of 0.27. The obtained resin had a HSP(boiling heptane soluble fraction) content of 35 wt. %; and a HIP(boiling heptane insoluble fraction) content of 65 wt. %. The HSP had anintrinsic viscosity of 1.95 dl/g and the HIP had an intrinsic viscosityof 4.78 dl/g.

Further, the obtained resin had a pentad fraction (rrrr/(1-mmmm))measured by ¹³ C-NMR, expressed as a percentage of 34.5%; a melting peaktemperature (Tm) measure by DSC of 158° C.; and an enthalpy of melting(ΔH) of 62.6 J/g. The domain structure was observed by a transmissiontype electron microscope. These results are as shown in Table 2.

Examples 13 to 15, and 18

The same procedures as in Example 12 were repeated to prepare a flexiblepolypropylene except that an ADMB/DPDMS ratio was changed to obtain adesired HSP/HIP ratio. The results are as shown in Table 2.

Example 16

In the same manner as in Example 12, a solid catalyst component wasprepared and then a solid component (A) was prepared.

In a 5 liter three-necked, pressure glass flask sufficiently purged withnitrogen, were charged 20 g of polypropylene powders, 3 mmol of AlEt₃,0.15 mmol of 1-allyl-3,4-dimethoxybenzene (ADMB), and 20 ml of heptanesolution containing 100 mg of the solid catalyst component (A) (0.06mmol: calculated in terms of Ti atom). After the reaction system wasevacuated for 5 minutes, propylene gas was supplied until the totalpressure of the reaction system reached 20 Kg/cm². The gas phasepolymerization was carried out at 50° C. for 17 hours, to obtain 350 gof a flexible polypropylene resin having a MI of 0.10. The obtainedresin had a HSP (boiling heptane soluble fraction) content of 41 wt. %;and a HIP (boiling heptane insoluble fraction) content of 59 wt. %. TheHSP had an intrinsic viscosity of 2.98 dl/g and the HIP had an intrinsicviscosity of 6.14 dl/g.

Further, the obtained resin had a pentad fraction (rrrr/1-mmmm) measuredby ¹³ C-NMR of 29.8%; a melting peak temperature (Tm) measure by DSC of158° C.; and an enthalpy of melting (ΔH) of 54.1 J/g. The domainstructure was observed by a transmission type electron microscope. Theseresults are as shown in Table 2.

Example 17

The same procedures as in Example 12 were repeated to prepare a flexiblepolypropylene resin except that the amount of cocatalyst forpolymerization and the like were changed to obtain a flexiblepolypropylene resin containing a HSP with a desired intrinsic viscosity.The results are as shown in Table 2.

Comparative Examples 5 to 7

The same procedures as in Example 12 were repeated to prepare a flexiblepolypropylene resin except that the amount of cocatalyst forpolymerization was changed to obtain a flexible polypropylene containinga HSP and a HIP at a specific ratio, the HSP having a desired intrinsicviscosity. The results are as shown in Table 2.

Examples 19

The same procedures as in Example 12 were repeated except that the solidproduct prepared by drying the product resulting from the followingreaction of metallic magnesium, ethanol and iodine was used instead ofMg(OEt)₂.

[Reaction of Metallic Magnesium, Ethanol and Iodine]

A glass reactor (inner Volume: 6 liter) equipped with a stirrer waspurged with nitrogen gas. To the reactor, were introduced 160 g ofmetallic magnesium, about 2430 g of ethanol and 16 g of iodine. Thereaction was carried out under heating and refluxing conditions whilethe reaction mixture was stirred until generation of hydrogen ended toobtain a reaction product. The results are as shown in Table 2.

Example 20

The same procedures as in Example 19 were repeated except that thereaction product of metallic magnesium, ethanol and iodine was usedwithout being dried, but filtered. The results are as shown in Table 2.

In addition, each physical property of the polymer was measured asfollows.

Intrinsic Viscosity [η]

The intrinsic viscosity was measured in a decaline solution at 135° C.

Tm and ΔH

The melting peak temperature (Tm: temperature at melting peak) wasmeasured by a differential thermal analysis measurement equipment(DSC-7: manufactured by Perkin-Elmer) in accordance with JIS-K7121.Further, the enthalpy of melting (ΔH: total amount of energy absorbed attime of melting of crystalline) was measured in accordance withJIS-K7122.

Domain Structure

A specimen was prepared by a RuO₄ dyeing method and ultra-thin platemethod. The domain structure was observed by a transmission typeelectron microscope (JEM-100CKII: Manufactured by Nihon Denshi Co.,Ltd.) at an acceleration voltage of 100 KV with a magnification of 1000to 60000.

rrrr/(1-mmmm)

JNM-FX-200 (Manufactured by Nihon Denshi Co., Ltd: ¹³ C-nuclearresonance frequency of 50.1 MHz) was used as measurement equipment. Themeasurement conditions were as follows.

Measurement Mode: Proton Complete Decoupling Method

Pulses Width: 6.9 microseconds

Pulse Repeating Time: 3 seconds

Integrating Times: 10000

Solvent: 1,2,4-trichlorobenzene/heavy benzene (90/10 Vol. %)

Concentration of Sample: 250 mg/2.5 ml Solvent

Measurement Temperature: 130° C.

Under the above measurement conditions, the pentad fraction is measuredusing a difference in chemical shift due to a stereoregularity of amethyl group. More specifically, the pentad fraction is calculated froman area strength ratio of each peak of mmmm to mrrm appearing in aregion of 22.5 to 19.5 ppm. In addition, the chemical shift of eachatmospheric methyl group, when tetramethylsilane (TMS) is used asstandard substance, is as follows.

    ______________________________________                                        mmmm           21.86 ppm                                                        mmmr 21.62 ppm                                                                mmrr 21.08 ppm                                                                mmrm + rrmr 20.89 ppm                                                         rrrr 20.36 ppm                                                                mrrm 19.97 ppm                                                              ______________________________________                                    

Melt Flow Rate (MI) Measurement

The melt flow rate was measured at 230° C. at a testing load of 2.16 Kgfin accordance with JIS-K7210.

Tensile Test

As a specimen, JIS 2 type dunbel (thickness of 1 mm; pressed article)was used, and the tensil strength was measured at a testing speed of 50mm/min. at 23° C. in accordance with JIS-K7113.

Izod Impact Strength Test

As a specimen, JIS 2 type A-punched plate (thickness of 3 mm; pressedarticel) was used, and the impact strength was measured under theconditions as indicated in the table in accordance with JIS-K7110.

                  TABLE 2 (1)                                                     ______________________________________                                        Polymer Formulation  Polymer Properties                                       (x)HSP Portion                                                                              (y)HIP Portion                                                                           rrrr/                                                [η]   Amount  [η]                                                                              Amount                                                                              (1-mmmmm)                                                                             Tm   ΔH                            (dl/g) (wt/%) (dl/g) (wt/%) (%) (° C.) (J/g)                         ______________________________________                                        Example                                                                              1.95   35      4.78 65    34.5    158  62.6                              12                                                                            Example 1.67 80 3.79 20 46.9 156 30.2                                         13                                                                            Example 1.70 56 4.37 44 40.2 155 33.9                                         14                                                                            Example 1.77 25 4.82 75 32.1 161 80.2                                         15                                                                            Example 2.98 41 6.14 59 29.8 158 53.3                                         16                                                                            Example 1.66 51 4.43 49 33.3 158 54.1                                         17                                                                            Comp. Ex. 0.63  5 4.42 95 2.3 165 110                                         5                                                                             Comp. Ex. 0.82 56 3.83 44 9.8 154 65.8                                        6                                                                             Example 1.63 15 4.71 85 30.5 166 95.2                                         18                                                                            Comp. Ex. 1.77 95 4.01  5 40.3 150 35.2                                       7                                                                             Example 1.95 35 4.78 65 34.5 158 62.6                                         19                                                                            Example 1.95 35 4.78 65 34.6 158 62.7                                         20                                                                          ______________________________________                                         Note: 1) unit: kg · cm/cm                                       

                                      TABLE 2 (2)                                 __________________________________________________________________________    Physical Properties            Domain                                                         Impact                                                                            Tensile                                                                            Heat  Structure                                        MI Izod Strength Strength Distortion Yes: ◯                       (g/10 min) 23° C. -20° C. (kg/cm.sup.2) Temp (°                                       C.) No: ×                                __________________________________________________________________________    Example 12                                                                          0.27 NB   3.2 5500 60.4  ◯                                    Example 13 0.41 NB 4.5 1000 55.0 ◯                                Example 14 0.45 NB 3.5 2800 60.1 ◯                                Example 15 0.03 NB 2.6 7000 65.1 ◯                                Example 16 0.10 NB 4.0 4500 60.0 ◯                                Example 17 0.79 NB 3.2 3200 60.3 ◯                                Comp. Ex. 5 0.12 1.8 1.4 16500  110 ×                                   Comp. Ex. 6 0.35 8.5 1.6 2800 50.2 ×                                    Example 18 0.10 NB 2.8 8500 66.2 ◯                                Comp. Ex. 7 0.63 NB 7.1 1000 35.0 ×                                     Example 19 0.27 NB 3.2 5500 60.4 ◯                                Example 20 0.27 NB 3.2 5500 60.4 ◯                              __________________________________________________________________________

Example 21

(1) Preparation of Solid Catalyst Component (A-b)

In a 500 ml three-necked glass flask sufficiently purged with nitrogen,were placed 20 ml of purified heptane, 4 g of Mg(OEt)₂ and 1.2 g ofdi-n-butyl phthalate. To the reaction mixture, 4 ml of TiCl₄ was addeddropwise while the temperature of the reaction system was kept at 90° C.111 ml of TiCl₄ was further added and then the reaction mixture washeated to 110° C. Then, the reaction was carried out at 110° C. for 2hours. Thereafter, the reaction product was washed with purified heptaneheated to 80° C. Then, 115 ml of TiCl₄ was added to the solid portion ofthe reaction product, and the reaction was further carried out at 110°C. for 2 hours. After completion of the reaction, the reaction productwas washed with 100 ml of purified heptane several times, to obtain asolid catalyst component.

(2) Preparation of Solid Component (A)

In a 2.5 liter three-necked, pressure glass flask sufficiently purgedwith nitrogen, were placed 1.7 liter of purified heptane, 0.07 mol ofAlEt₃, 0.05 mmol of diphenyldimethoxysilane (DPDMS) and 12.0 g of thesolid catalyst component obtained in the above Preparation (1). Then,the reaction system was kept at 30° C. and under an inner pressure of0.5 g/cm².G by continuously adding propylene while the reaction mixturewas stirred. The reaction was carried out for one hour. Then, thereaction product was purified 5 times with 1 liter of purified heptaneto prepare a solid catalyst component (A).

(3) Gas Phase One-Step Polymerization

In a 5 liter stainless, pressure autoclave, were placed 20 g ofpolypropylene powders, 3 mmol of AlEt₃, 0.15 mmol of1-allyl-3,4-dimethoxybenzene (ADMB), 0.23 mmol ofdiphenyldimethoxysilane (DPDMS) and 20 ml of heptane solution containing100 mg of the solid catalyst component (A) (0.06 mmol: calculated interms of Ti atom). After the reaction system was evacuated for 5minutes, propylene gas was supplied until the total pressure of thereaction system reached 28 Kg/cm². Then, the gas phase polymerizationwas carried out at 70° C. for 1.7 hours.

(4) Gas Phase Two-Step Polymerization

After completion of the reaction in the above (3), the reaction systemwas depressurized and evacuated. Then, a mixed gas of ethylene andpropylene (mol ratio of 1/4) was added to the reaction system until thepressure reached 10 Kg/cm². Thereafter the gas phase polymerization wascarried out at 50 ° C. for 1.4 hours, to obtain 550 g of a propylenebased elastomer having a Melt Index (MI) of 0.1 g/10 min. The obtainedelastomer was composed of 65 wt. % of a polypropylene homopolymer and 35wt. % of an ethylene/propylene copolymer. The homopolymer contained 35wt. % of HSP (boiling heptane soluble fraction) having an intrinsicviscosity of 1.95 dl/g and 65 wt. % of HIP (boiling heptane insolublefraction) having an intrinsic viscosity of 4.78 dl/g. The obtainedelastomer had a pentad fraction (rrrr/(1-mmmm)) measured by ¹³ C-NMR,expressed as a percentage, of 34.5%; a melting peak temperature (Tm)measured by DSC of 158° C.; and an enthalpy of melting (ΔH) of 62.6 J/g.The domain structure was observed by a transmission type electronmicroscope. On the other hand, the copolymer had an ethylene unitcontent of 31 mol % and an intrinsic viscosity of 4.81 dl/g.

Examples 22 to 24, 32 and 33 and Comparative Examples 8 and 10

The same procedures as in Example 21 were repeated except that the ratioof ADMB/DPDMS was changed to obtain a resin having specific HSP content.

Examples 25 to 27 and Comparative Example 9

The same procedures as in Example 21 were repeated except that thehydrogen concentration was changed to obtain a resin having a HSP withprescribed intrinsic viscosity.

Examples 28, 29, 34 and 35 and Comparative Example 11

The same procedures as in Example 21 were repeated except that thepolymerization time for the second polymerization step was changed toobtain a resin having a prescribed ratio of component (o) and component(p) or (p').

Example 30

Blending Method

The propylene homopolymer synthesized in Example 21 and a EP rubber weremelt-blended.

(1) Propylene Homopolymerization by Gas Phase Method

In a 5 liter stainless, pressure autoclave, were placed 20 g ofpolypropylene powders, 3 mmol of AlEt₃, 0.15 mmol of1-allyl-3,4-dimethoxybenzene (ADMB), 0.23 mmol ofdiphenyldimethoxysilane (DPDMS) and 20 ml of heptane solution containing100 mg of the solid catalyst component (A) (prepared in Example 21 (2);0.06 mmol as calculated in terms of Ti atom). After the reaction systemwas evacuated for 5 minutes, propylene gas was supplied until the totalpressure of the reaction system reached 28 Kg/cm². Then, the gas phasepolymerization was carried out at 70° C. for 1.7 hours.

(2) Melt-Blending of Propylene Homopolymer and EP Rubber

In a laboplast mil having an inner volume of 30 ml, 13 g of propylenehomopolymer obtained in Preparation (1) and 7 g of an ethylene/propylenecopolymer rubber (Manufactured by Nippon Synthetic Rubber; TradenameEP02P) at a rotation of 70 rpm at 195° C. for 2 hours, to obtain 20 g ofan elastomer having a Melt Index of 0.5 g/10 min. The obtained elastomerwas composed of 65 wt. % of a polypropylene homopolymer and 35 wt. % ofan ethylene/propylene copolymer. The homopolymer contained 35 wt. % ofHSP (boiling heptane soluble fraction) having an intrinsic viscosity of1.95 dl/g and 65 wt. % of HIP (boiling heptane insoluble fraction)having an intrinsic viscosity of 4.78 dl/g. The ethylene/propylenecopolymer had an ethylene unit content of 73.1 mol % and an intrinsicviscosity of 1.37 dl/g. The results of evaluation of the pressed articleof the obtained blend are as shown in Table 3.

Example 31

The same procedures as in Example 30 were repeated except that anethylene/propylene rubber (Nihon Synthetic Rubber Co., Ltd.: TradenameEP07P) having an ethylene unit content of 71.3 mol % and an intrinsicviscosity of 1.97 dl/g was used as the ethylene propylene rubber.

Example 36

(1) Gas Phase One-Step Polymerization

In a 5 liter stainless, pressure autoclave, were placed 20 g ofpolypropylene powders, 2 mmol of AlEt₃, 0.5 mmol ofdiphenyldimethoxysilane (DPDMS) and 20 ml of heptane solution containing17 mg of the solid catalyst component (A) of Example 17 (0.06 mmol ascalculated in terms of Ti atom). After the reaction system was evacuatedfor 5 minutes, propylene gas was supplied until the total pressure ofthe reaction system reached 31 Kg/cm². Then, the gas phasepolymerization was carried out at 70° C. for 1.7 hours.

(2) Gas Phase Two-Step Polymerization

After completion of the reaction in the above (1), the reaction systemwas depressurized and evacuated. Then, nitrogen gas was introducedthereto until inner pressure reached normal pressure. Thereafter, 3.8 ml(30 mmol) of dicyclopentadiene was added and the reaction system wasevacuated. Then, a mixed gas of ethylene and propylene (mol ration of2/3) was added to the reaction system until the pressure reached 10Kg/cm². Then, the gas phase polymerization was carried out at 50° C. for1.4 hours, to obtain 540 g of a flexible polypropylene having a MeltIndex (MI) of 0.1 g/10 min. The obtained polypropylene was composed of65 wt. % of a polypropylene homopolymer and 35 wt. % of anethylene/propylene copolymer. The homopolymer contained 35 wt. % of HSP(boiling heptane soluble fraction) having an intrinsic viscosity of 1.95dl/g and 65 wt. % of HIP (boiling heptane insoluble fraction) having anintrinsic viscosity of 4.78 dl/g. The polypropylene had a pentadfraction (rrrr/(1-mmmm)), measured by ¹³ C-NMR, expressed as apercentage, of 34.5%; a melting peak temperature (Tm) measured by DSC of158° C.; and an enthalpy of melting (Δ) of 62.6 J/g. The domainstructure was observed by a transmission type electron microscope. Onthe other hand, the copolymer had an ethylene unit content of 31 mol %;a polyene unit content of 35 wt. %; and an intrinsic viscosity of 4.79dl/g.

Example 37

The same procedures as in Example 21 were repeated except that the solidproduct prepared by drying the product resulting from the followingreaction of metallic magnesium, ethanol and iodine was used instead ofMg(OEt)₂.

[Reaction of Metallic Magnesium, Ethanol and Iodine]

A glass reactor (inner Volume: 6 liter) equipped with a stirrer waspurged with nitrogen gas. To the reactor, were introduced 160 g ofmetallic magnesium, about 2430 g of ethanol and 16 g of iodine. Thereaction was carried out under heating and refluxing conditions whilethe reaction mixture was stirred until generation of hydrogen ended toobtain a reaction product.

Example 38

The same procedures as in Example 37 were repeated except that thereaction product of metallic magnesium, ethanol and iodine was usedwithout being dried, but filtered.

The results of the above examples and comparative examples are as shownin Table 3. The following test was conducted in addition to theevaluation as described above.

Shore Hardness D (Durometer D Hardness)

                                      TABLE 3(1)                                  __________________________________________________________________________           Propylene Based Elastomer Composition (o + p)                                 Polypropylene (o)                                                                      Property                                                             HSP Portion          Domain                                                                             HIP Portion                                             Intrinsic                                                                          rrrr/       Structure                                                                              Intrinsic                                  Amount Viscosity (l-mmmm) Tm ΔH Yes: ∘ Amount                                                       Viscosity Amount                      (wt %) (g/dl) (%) (C.°) (J/g) No: X (wt %) (g/dl) (wt %)             __________________________________________________________________________    Example 21                                                                           35  1.95 34.5  158                                                                              62.6                                                                             ∘                                                                      65  4.78 65                                    Example 22 45 2.01 37.3 157 45.2 ∘ 55 4.13 60                     Example 23 50 1.98 38.6 157 35.5 ∘ 50 4.45 63                     Example 24 65 2.03 42.5 155 31.5 ∘ 35 4.15 65                     Comp. Ex. 8 5 1.9 2.3 165 110 X 95 3.00 65                                    Example 25 35 2.98 34.5 158 58 ∘ 65 6.14 70                       Example 26 40 2.41 35.6 158 60.3 ∘ 60 5.42 65                     Example 27 36 2.25 34.5 158 61.5 ∘ 64 4.37 67                     Comp. Ex. 9 35 1.09 9.8 154 65.8 X 65 1.64 65                                 Example 28 35 1.99 34.4 158 62.5 ∘ 65 4.13 75                     Example 29 35 1.95 34.5 158 62.6 ∘ 65 4.78 45                     Example 30 35 1.95 34.5 158 62.6 ∘ 65 4.78 65                     Example 31 35 1.95 34.5 158 62.6 ∘ 65 4.78 65                     Example 32 15 1.53 25.2 156 85.2 ∘ 85 4.33 65                     Example 33 85 2.25 46.9 156 30.2 ∘ 15 4.37 63                     Comp. Ex. 10 92 1.3 9.8 150 25.4 X 8 1.95 61                                  Example 34 35 1.95 34.5 168 62.6 ∘ 65 4.78 15                     Example 35 38 1.97 34.5 158 62.4 ∘ 62 4.78 85                     Comp. Ex. 11 36 1.98 34.5 158 62.4 ∘ 64 4.78 97                   Example 36 35 1.95 34.5 158 62.6 ∘ 65 4.78 65                     Example 37 35 1.95 34.5 158 62.6 ∘ 65 4.78 65                     Example 38 35 1.95 34.5 158 62.6 ∘ 65 4.78 65                   __________________________________________________________________________

As a specimen, a 3 mm thick plate (pressed article) was used, and thehardness was measured at 23° C. in accordance with JIS-K7215.

                                      TABLE 3(2)                                  __________________________________________________________________________                         Physical Properties                                                                                   Izod                               Copolymer Formulation     Tensile Impact                                      Component (P) or (P')  Yield Fracture  Elasti- Strength/                           Ethylene                                                                           Intrinsic                                                                              MI Shore                                                                              Stress                                                                           Stress                                                                            Elongation                                                                         city                                                                              20° C.                      Content viscosity Amount (g/10 Hardness (kg/ (kg/ at Break (kg/ (kg/                                                      (wt %) (g/dl) (wt %) min)                                                    (D Scale) cm.sup.2) cm.sup.2)                                                  (%) cm.sup.2) cm/cm)            __________________________________________________________________________    Example 21                                                                           31   4.81 35  0.1                                                                              55   -- 200 500  2500                                                                              N B                                Example 22 30 4.77 40 0.1 54 -- 150 510 2000 N B                              Example 23 30 4.8 37 0.1 50 -- 120 480 1810 N B                               Example 24 31 4.75 35 0.1 50 -- 100 500 1600 N B                              Comp. Ex. 8 30 4.88 35 0.1 90 220 80 120 11000  5.2                           Example 25 35 4.8 30 0.05 58 -- 200 230 2500 N B                              Example 26 30 4.79 35 0.08 55 -- 180 500 2300 N B                             Example 27 32 4.74 33 0.1 57 -- 200 510 2000 N B                              Comp. Ex. 9 31 4.52 35 0.5 60 150 50 210 5000  5.0                            Example 28 30 4.7 25 0.1 53 -- 250 520 3000 N B                               Example 29 29 4.8 55 0.1 50 -- 100 480 1500 N B                               Example 30 73.1 1.37 35 0.5 55 -- 170 450 2500 N B                            Example 31 71.3 1.97 35 0.3 55 -- 190 500 2300 N B                            Example 32 30 4.87 35 0.2 58 80 260 310 7500 19.2                             Example 33 31 4.66 37 0.1 50 -- 100 540 1200 N B                              Comp. Ex. 10 30 4.6 39 0.2 40 --  80 500 8000 N B                             Example 34 30 4.5 85 0.1 48 -- 150 550 1000 N B                               Example 35 33 4.61 15 0.1 59 -- 260 500 5300 20.1                             Comp. Ex. 11 30 4.5 3 0.2 65 150 360 540 5500  2.1                            Example 36 31 4.79 35 0.1 54 -- 190 510 2400 N B                              Example 37 31 4.81 35 0.1 55 -- 200 500 2500 N B                              Example 38 31 4.81 35 0.1 55 -- 200 500 2500 N B                            __________________________________________________________________________

Example 39

(1) Preparation of Solid Catalyst Component (A-b)

In the same manner as in Example 21, a solid catalyst component (A-b)was prepared.

(2) Preparation of Solid Component (A)

In the same manner as in Example 21 (2), a solid component (A) wasprepared.

(3) Gas Phase One-Step Polymerization

In the same manner as in Example 21 (3), the gas phase one-steppolymerization was conducted.

The working conditions are as shown in Table 4.

As a result of the above polymerization, 370 g of polypropylenehomopolymer having a Melt Index (MI) of 0.07 g/10 min. was obtained. Theobtained polymer had a HSP (boiling heptane soluble fraction) content of35.1 wt. %; an intrinsic viscosity of 1.95 dl/g; and a bulk density of0.33 g/dl. The powder properties of the obtained product were alsoexcellent. The results are as shown in Table 4.

Examples 40 to 42

The same procedures as in Example 39 were repeated except that theamount of 1-allyl-3,4-dimethoxybenzene (ADMB), Component (C) of thecatalyst system and the amount of dimethoxydiphenylsilane (DMDPS),Component (D) were changed.

Examples 43 to 45

The same procedures as in Example 39 were repeated except that the kindsof Components (C) and (D) of the catalyst system were changed.

Examples 46 and 47

The same procedures as in Example 39 were repeated except that hydrogenwas added during the polymerization.

Examples 48 and 49

The same procedures as in Example 39 were repeated except that thereaction temperature was changed.

Examples 50 to 52

The same procedures as in Example 39 were repeated except that theamount and/or kinds of the component (A) of the catalyst system waschanged.

Example 53

The same procedures as in Example 39 were repeated except that a solidcomponent (A) was prepared in the following manner.

Into a 0.5 liter stainless, pressure autoclave, were introduced 0.4liter of purified heptane, 90 g of polypropylene powders, 0.01 mol ofAlEt₃, 0.005 mol of diphenyldimethoxysilane (DPDMS) and 30 g of thesolid catalyst component (A-b) while the mixture was stirred. Afterstirring the mixture for 15 minutes, a supernatant was removed. Then,the resultant product was vacuum dried to obtain a solid component (A).

Comparative Example 12

The same procedures as in Example 39 were repeated except that thecomponent (D) (DMDPS) of the catalyst system was not added.

Comparative Example 13

The same procedures as in Example 39 were repeated except that thecomponent (C) (ADMB) of the catalyst system was not added.

The working conditions and the results of Examples 39 to 53 andComparative Examples 12 and 13 are as shown in Table 4.

Example 54

(1) Preparation of Solid Catalyst Component (A-b)

In the same manner as in Example 21, a solid catalyst component (A-b)was prepared.

(2) Preparation of Solid Component (A)

In the same manner as in Example 21 (2), a solid component (A) wasprepared.

(3) Gas Phase One-Step Polymerization

In the same manner as in Example 21 (3), the gas phase one-steppolymerization was conducted.

(4) Gas Phase Two-Step Polymerization

After completion of the reaction in the above (3), the reaction systemwas depressurized and evacuated. Then, a mixed gas of ethylene andpropylene (mol ratio of 1/4) was added to the reaction system until thepressure reached 11 Kg/cm². Then, the gas phase polymerization wascarried out at 50° C. for 1.4 hours.

The working conditions are as shown in Table 5.

There was obtained 810 g of an ethylene/propylene block copolymer havinga Melt Index (MI) of 0.1 g/10 min. The obtained copolymer was composedof 65 wt. % of a polypropylene homopolymer having an intrinsic viscosityof 3.86 dl/g; and 35 wt. % of an ethylene/propylene block copolymerhaving an intrinsic viscosity of 4.81 dl/g. The results are as shown inTable 6.

Examples 55 to 57

The same procedures as in Example 54 were repeated except that thepolymerization time for the second polymerization step was changed. Theresults are as shown in Table 3.

Examples 58 and 59

The same procedures as in Example 54 were repeated except that the ratioof the gas components was changed.

Examples 60 to 62

The same procedures as in Example 54 were repeated except that hydrogenwas added during the polymerization.

Comparative Example 14

The same procedures as in Example 54 were repeated except that thecomponent (C) (ADMB) for the catalyst system was not added.

The working conditions and the results of Examples 54 to 62 andComparative Example 14 are as shown in Table 5 and Table 6,respectively.

The polymer compositions obtained in Examples 54 to 62 and ComparativeExample 14 were evaluated in physical properties such as Melt Index,Shore hardness, yield stress, fracture stress, elongation at break,tensile elastic modulus and izod impact strength value. The results ofmeasurements are as shown in Table 6. In addition, each measurement wasconducted in the same manner as above.

                                      TABLE 4(1)                                  __________________________________________________________________________           Catalyst Components                                                           Component (A)                  Ti atom in                                            (A - a)/                                                                           Component C*.sup.2                                                                     Component D*.sup.2                                                                      (C)/(A)                                                                             (C)/(D)                                  (A - a)                                                                              (A - b)  Amount    Amount                                                                             (mmol/                                                                              (mmol/                              Kind (wt/wt) Kind (mmol) Kind (mmol) mmol) mmol)                            __________________________________________________________________________    Example 39                                                                           Polypropylene                                                                        3.2  ADMB                                                                              0.150                                                                              DMDPS                                                                              0.230                                                                              7.6   0.65                                Example 40 " " " 0.150 " 0.115 " 1.30                                         Example 41 " " " 0.150 " 0.300 " 0.50                                         Example 42 " " " 0.170 " 0.45. 8.6 0.38                                       Example 43 " " " 0.150 PTES 0.230 7.6 0.65                                    Example 44 " " " 0.150 TMPi 0.230 " 0.65                                      Example 45 " " DMB 0.150 DMDPS 0.230 " 0.65                                   Comp. Ex. 12 " " ADMB 0.150 -- -- " --                                        Comp. Ex. 13 " " -- -- DMDPS 0.230 -- --                                      Example 46 " " ADMB 0.150 DMDPS 0.230 7.5 0.65                                Example 47 " " " 0.150 " " " "                                                Example 48 " " " 0.150 " 0.230 " "                                            Example 49 " " " 0.150 " " " "                                                Example 50 " 5.0 " 0.150 " 0.230 " "                                          Example 51 " 1.6 " " " " " "                                                  Example 52 Polyethylene 3.2 " " " " " "                                       Example 53 Polypropylene " " " " " " "                                      __________________________________________________________________________     *.sup.1 DMDPS; dimethoxydiphenylsilane PTES; phenyltriethoxysilane TMPi;      2,2,6,6tetramethylpiperadine                                                  *.sup.2 ADMB; 1allyl-3,4-dimethoxybenzene DMB; Odimethoxybenzene              *.sup.3 ⊚; Solid, almost no adhered matter, good powder        flowability                                                                   ∘; Solid, little adhered matter, but good powder flowability      X; Solid, lots of adhered matter, no powder flowability                  

                                      TABLE 4(2)                                  __________________________________________________________________________           Polymerization                                                           Conditions Results of Polymerization                                               Polymerization                                                                        H.sub.2    HSP Portion                                                                            Bulk                                              Temperature                                                                           Amount                                                                             MI    Amount                                                                             [μ]                                                                            Density                                                                            Powder*.sup.3                           (° C.) (kg/cm.sup.2) (g/10 min) (wt %) (dl/g) (g/cc) Properties      __________________________________________________________________________    Example 39                                                                           70      --   0.07  35.1 1.95                                                                              0.33 ⊚                        Example 40 " -- " 39.1 1.95 0.32 ⊚                             Example 41 " -- " 25.0 1.77 0.34 ⊚                             Example 42 " -- " 16.1 1.69 0.34 ⊚                             Example 43 " -- " 34.2 1.98 0.33 ⊚                             Example 44 " -- " 39.3 2.03 0.31 ⊚                             Example 45 " -- " 36.2 1.53 0.32 ⊚                             Comp. Ex. 12 " -- " 50.1 1.99 N/A X                                           Comp. Ex. 13 " -- " 1.5 0.45 0.39 ⊚                            Example 46 " 0.2 1.1  38.7 1.90 0.29 ∘                            Example 47 " 0.4 7.1  40.4 1.81 0.28 ∘                            Example 48 75 -- 0.07 37.8 1.89 0.30 ⊚                         Example 49 65 -- " 32.0 1.97 0.35 ⊚                            Example 50 70 -- " 35.0 1.96 0.33 ⊚                            Example 51 " -- " 34.8 1.97 0.29 ∘                                Example 52 " -- " 35.1 1.94 0.33 ⊚                             Example 53 " -- " 34.3 1.96 0.33 ⊚                           __________________________________________________________________________

                                      TABLE 5(1)                                  __________________________________________________________________________           Catalyst Components                                                           Component A                     Ti atom in                                            (A - a)/                                                                           Component C*.sup.1                                                                     Component D*.sup.2                                                                      (C)/(A)                                                                             (C)/(D)                                 (A - a) (A - b)  Amount    Amount                                                                             (mmol/                                                                              (mmol/                             Kind (wt/wt) Kind (mmol) Kind (mmol) mmol) mmol)                            __________________________________________________________________________    Example 54                                                                           Polypropylene                                                                         3.2  ADMB                                                                              0.15 DPDMS                                                                              0.23 7.6   0.33                               Example 55 " " " " " " " "                                                    Example 56 " " " " " " " "                                                    Example 57 " " " " " " " "                                                    Example 58 " " " " " " " "                                                    Example 59 " " " " " " " "                                                    Comp. Ex. 14 " " -- -- " " -- --                                              Example 60 " " ADMB 0.15 " " 7.6 0.33                                         Example 61 " " " " " " " "                                                    Example 62 " " " " " " " "                                                  __________________________________________________________________________     *.sup.1 ADMB = 1allyl-3,4-dimethoxybenzene                                    *.sup.2 DPDMS = diphenyldimethoxysilane                                  

                                      TABLE 5(2)                                  __________________________________________________________________________           Polymerization Conditions                                                     1st Step Polymerization                                                                        2nd Step Polymerization                                      Polymerization                                                                       Polymerization                                                                       H.sub.2                                                                          Polymerization                                                                       Polymerization                                                                       H.sub.2                                                                          C.sub.2 /C.sub.3                       Temperature Time (kg/ Temperature Time (kg/ (mmol/                            (° C.) (hr) cm.sup.2) (° C.) (hr) cm.sup.2) mmol)             __________________________________________________________________________    Example 54                                                                           70     1.7    0  50       1.4  0  0.25                                   Example 55 " " " " 0.8 " "                                                    Example 56 " " " " 4.2 " "                                                    Example 57 " " " " 2.4 " "                                                    Example 58 " " " " 1.4 " 0.43                                                 Example 59 " " " " " " 0.30                                                   Comp. Ex. 14 " " " " " " 0.25                                                 Example 60 " " " " " 0.5 "                                                    Example 61 " " 0.5 " " 0.5 "                                                  Example 62 " " 0.5 " " 0.5 "                                                __________________________________________________________________________

                  TABLE 6 (1)                                                     ______________________________________                                                Polymer Formation                                                               Polypropylene                                                                             Copolymer Component                                             Component          Ethylene                                                  [η]                                                                              Amount  [η]  Content                                                                              Amount                                    (dl/g) (wt %) (dl/g) (wt %) (wt %)                                          ______________________________________                                        Example 54                                                                             3.86     65      4.81   31     35                                      Example 55 3.82 75 4.75 30 25                                                 Example 56 3.89 45 4.80 29 55                                                 Example 57 3.85 55 4.77 30 45                                                 Example 58 3.86 70 4.65 40 30                                                 Example 59 3.80 65 4.80 25 35                                                 Comp. Ex. 14 4.01 65 4.35 30 35                                               Example 60 3.65 70 1.75 31 30                                                 Example 61 1.76 72 5.19 30 28                                                 Example 62 1.74 79 1.77 30 21                                               ______________________________________                                    

                                      TABLE 6 (2)                                 __________________________________________________________________________           Physical Properties                                                           Melt                          Izod                                       Index Shore Yield Fracture Elongation Tensile Test Value                      MI Hardness Stress Stress at Break Elasity (-20° C.)                   (g/10 min) D Scale (kg/cm.sup.2) (kg/cm.sup.2) (%) (kg/cm.sup.2)                                                 (kgcm/cm)                                __________________________________________________________________________    Example 54                                                                           0.1  55   --   200  500  2500 NB                                         Example 55 0.1 53 -- 250 520 3000 NB                                          Example 56 0.1 50 -- 100 480 1500 NB                                          Example 57 0.1 50 -- 110 420 2000 NB                                          Example 58 0.1 55 -- 210 550 2600 NB                                          Example 59 0.1 54 -- 200 530 2500 NB                                          Comp. Ex. 14 0.1 90 220  60 100 13000  4.7                                    Example 60 0.5 50 -- 110 330 2000 NB                                          Example 61 1.1 54  80 150 450 2800 NB                                         Example 62 3.9 56 100 180 500 3700 5.1                                      __________________________________________________________________________

[Industrial Applicability]

According to the first embodiment of the present invention, atacticpolypropylene with high molecular weight and with narrow molecularweight distribution is blended with crystalline isotactic polypropylenein a specific ratio, to readily improve dynamic properties and hardnessof the isotactic polypropylene and to obtain a less expensive, flexiblepolypropylene resin with excellent dynamic properties as thermoplasticelastomer without cross-linking treatment.

Further, according to the first embodiment of the present invention,propylene is polymerized by a gas phase one-step polymerization methodor a slurry one-step polymerization method using a specific catalystsystem, to obtain a less expensive, flexible polypropylene resin withdynamic properties which are about the same as those of partiallycross-linked olefin based thermoplastic elastomer (TPO), without beingsubjected to cross-linking treatment.

These flexible polypropylene resins are superior in melting propertiesand are thus superior in injection-moldability as well asextrusion-moldability.

According to the second embodiment of the present invention, there isprovided a less expensive, propylene based elastomer having practicaltensile strength even when not vulcanized, good flexibility, andsufficient low temperature properties and low surface tackiness.

According to the third embodiment of the present invention, there isprovided a less expensive, olefin polymer having practical tensilestrength even when not vulcanized, good flexibility, and sufficient lowtemperature properties and low surface tackiness.

The flexible polypropylene resins and propylene based elastomersaccording to the present invention, can be molded into molded articles,by conventional molding techniques, which can be used for severalapplications.

In the case of injection-molding, molded articles can be suitably usedas exterior parts for automotive because of good flexibility, goodpaintability, good moldability, good scuff resistance and good impactstrength at low temperature. More specifically, the exterior partsinclude bumper, mole, mat guards for paint, side shields and spoilers.

In the case of hollow-molding, the molded articles can be suitably usedas parts which are likely to have different wall thickness, when madefrom conventional polypropylene, such as snake body shape portion of aduct or materials for deep-drawing because of good moldability.

In the case of extrusion-molding, the molded articles can suitably usedas sheets for under cover of engine because of good impact strength andgood heat resistance. For example, ceiling materials, inner lining of atrunk room, surface skin material for inner panels. The molded articlescan be used as insulating sheets in electrical part fields because ofgood processability and insulating properties. The molded articles canbe used as flexible codes, booster cables and the like in electric cablefields because of good heat resistance, good weatherability and goodanti-abrasion properties. The molded articles can also be used as waterproof sheets, water stopping materials or filling materials in theconstruction or construction material fields.

The polypropylene resins-can be used to make a laminate with the otherresins to obtain sheets which meet several needs.

We claim:
 1. A propylene based elastomer composition which comprises:(o)10 to 95 weight % of a polypropylene composition having a pentadfraction (rrrr/(1-mmmm)), measured by ¹³ C-NMR, expressed as apercentage, of not less than 20% and a domain structure which isobserved by a transmission type electron microscope, said compositioncomprising 10 to 90 weight % of boiling heptane soluble polypropylenehomopolymer having an intrinsic viscosity of not less than 1.2 dl/g and90 to 10 weight % of boiling heptane insoluble polypropylene homopolymerhaving an intrinsic viscosity of 0.5 to 9.0 dl/g; and (p) 90 to 5 weight% of an ethylene/propylene copolymer having an ethylene unit content of10 to 60 mol % and an intrinsic viscosity of 0.5 to 7.0 dl/g, allintrinsic viscosities being measured in a decaline solution at 135° C.2. The propylene based elastomer composition according to claim 1, whichhas an elongation at break of not less than 300%; a fracture stress ofnot less than 100 kg/cm² ; and a tensile elasticity of not more than8000 kg/cm², when measured at a testing speed of 50 mm/min. at 23° C. 3.A propylene based elastomer composition which comprises:(o) 10 to 90weight % of a polypropylene composition having a pentad fraction(rrrr/(1-mmmm)), measured by ¹³ C-NMR, expressed as a percentage, of notless than 20% and a domain structure which is observed by a transmissiontype electron microscope, said polymer comprising 10 to 90 weight % ofboiling heptane soluble polypropylene homopolymer having an intrinsicviscosity of not less than 1.2 dl/g and 90 to 10 weight % of boilingheptane insoluble polypropylene homopolymer having an intrinsicviscosity of 0.5 to 9.0 dl/g; and (p') an ethylene/propylene/polyenecopolymer having an ethylene unit content of 10 to 60 mol %, a polyeneunit content of 1 to 10 mol %, and an intrinsic viscosity of 0.5 to 7.0dl/g, all intrinsic viscosities being measured in a decaline solution at135° C.
 4. The propylene based elastomer composition according to claim3, which has an elongation at break of not less than 300%, a fracturestress of not less than 100 kg/cm² ; and a tensile elasticity of notmore than 8000 kg/cm², when measured at a testing speed of 50 mm/min. at23° C.
 5. A propylene based elastomer composition which comprises:(o) 10to 95 weight % of a polypropylene composition having a pentad fraction(rrrr/(1-mmmm)), measured by ¹³ C-NMR, expressed as a percentage, of notless than 20% and a domain structure which is observed by a transmissiontype electron microscope, said polymer comprising 10 to 90 weight % ofboiling heptane soluble polypropylene homopolymer having an intrinsicviscosity of not less than 1.2 dl/g and 90 to 10 weight % of boilingheptane insoluble polypropylene homopolymer having an intrinsicviscosity of 0.5 to 9.0 dl/g; and (p) 90 to 5 weight % of anethylene/propylene copolymer having an ethylene unit content of 10 to 60mol % and an intrinsic viscosity of 0.5 to 7.0 dl/g, all intrinsicviscosities being measured in a decaline solution at 135° C., whereinsaid polypropylene composition is formed by polymerization in thepresence of a catalyst system containing (A) a solid component including(a) crystalline polyolefin and (b) a solid catalyst component consistingof magnesium, titanium, a halogen atom and an electro donor; (B) anorganoaluminum compound; (C) an alkoxy group-containing aromaticcompound represented by the general formula: ##STR4## wherein R¹ is aC₁₋₂₀ alkyl group: R² is a C₁₋₁₀ hydrocarbon group, a hydroxy group or anitro group; m is an integer of 1 to 6: and n is 0 or an integer of 1 to(6-m); and (D) an electron donative compound.
 6. A propylene basedelastomer composition which comprises:(o) 10 to 90 weight % of apolypropylene composition having a pentad fraction (rrrr/(1-mmmm)),measured by ¹³ C-NMR, expressed as a percentage, of not less than 20%and a domain structure which is observed by a transmission type electronmicroscope, said polymer comprising 10 to 90 weight % of boiling heptanesoluble polypropylene homopolymer having an intrinsic viscosity of notless than 1.2 dl/g and 90 to 10 weight % of boiling heptane insolublepolypropylene homopolymer having an intrinsic viscosity of 0.5 to 9.0dl/g; and (p') an ethylene/propylene/polyene copolymer having anethylene unit content of 10 to 60 mol %, a polyene unit content of 1 to10 mol %, and an intrinsic viscosity of 0.5 to 7.0 dl/g, all intrinsicviscosities being measured in a decaline solution at 135° C.,whereinsaid polypropylene composition is formed by polymerization in thepresence of a catalyst system containing (A) a solid component including(a) crystalline polyolefin and (b) a solid catalyst consisting ofmagnesium, titanium, a halogen atom and an electron donor; (B) anorganoaluminum compound; (C) an alkoxy group-containing aromaticcompound represented by the general formula: ##STR5## wherein R¹ is aC₁₋₂₀ alkyl group: R² is a C₁₋₁₀ hydrocarbon group, a hydroxy group or anitro group; m is an integer of 1 to 6: and n is 0 or an integer of 1 to(6-m); and (D) an electron donative compound.
 7. The propylene basedelastomer composition according to claim 1, wherein said polypropylenecomposition consists of homopolymers.
 8. The propylene based elastomercomposition according to claim 1, containing 40-80 wt. % of saidpolypropylene composition, and 20-60 wt. % of the ethylene/propylenecopolymer.
 9. The propylene based elastomer composition according toclaim 1, wherein the boiling heptane soluble polypropylene has anintrinsic viscosity of at least 1.5 dl/g, the boiling heptane insolublepolypropylene has an intrinsic viscosity of 1.0 to 6.0 dl/g, and theethylene/propylene copolymer has an -intrinsic viscosity of 1.0 to 3.0dl/g.
 10. The propylene based elastomer composition according to claim2, wherein said elongation is at least 400%; said fracture stress is atleast 150 kg/cm² ; and said tensile elasticity is at most 5000 kg/cm².11. The propylene based elastomer composition according to claim 3,wherein said polypropylene composition consists of homopolymers.
 12. Thepropylene based elastomer composition according to claim 3, containing40-80 wt. % of said polypropylene composition and 20-60 wt. % of saidethylene/propylene/polyene copolymer.
 13. The propylene based elastomercomposition according to claim 3, wherein the boiling heptane solublepolypropylene has an intrinsic viscosity of at least 1.5 dl/g, theboiling heptane insoluble polypropylene has an intrinsic viscosity of1.0 to 6.0 dl/g, and the ethylene/propylene/polyene copolymer has anintrinsic viscosity of 1.0 to 3.0 dl/g.
 14. The propylene basedelastomer composition according to claim 4, wherein said elongation isat least 400%; said fracture stress is at least 150 kg/cm² ; and saidtensile elasticity is at most 5000 kg/cm².
 15. The propylene basedelastomer composition according to claim 5, wherein said polypropylenecomposition consists of homopolymers.
 16. The propylene based elastomercomposition according to claim 5, containing 40-80 wt. % of saidpolypropylene composition, and 20-60 wt. % of the ethylene/propylenecopolymer.
 17. The propylene based elastomer composition according toclaim 5, wherein the boiling heptane soluble polypropylene has anintrinsic viscosity of at least 1.5 dl/g, the boiling heptane insolublepolypropylene has an intrinsic viscosity of 1.0 to 6.0 dl/g, and theethylene/propylene copolymer has an intrinsic viscosity of 1.0 to 3.0dl/g.
 18. The propylene based elastomer composition according to claim6, wherein said polypropylene composition consists of homopolymers. 19.The propylene based elastomer composition according to claim 6,containing 40-80 wt. % of said polypropylene composition and 20-60 wt. %of said ethylene/propylene/polyene copolymer.
 20. The propylene basedelastomer composition according to claim 6, wherein the boiling heptanesoluble polypropylene has an intrinsic viscosity of at least 1.5 dl/g,the boiling heptane insoluble polypropylene has an intrinsic viscosityof 1.0 to 6.0 dl/g, and the ethylene/propylene/polyene copolymer has anintrinsic viscosity of 1.0 to 3.0 dl/g.